Polycarbonate based polyols

ABSTRACT

A method of manufacturing a poly(ether-carbonate) polyol comprises a polymerization stage that includes polymerizing carbon dioxide and at least one alkylene oxide, with a starter, in the presence of a double metal cyanide polymerization catalyst and a catalyst promoter that is devoid of halide anions and cyanide. The catalyst promoter is separate from the double metal cyanide polymerization catalyst.

FIELD

Embodiments relate to polycarbonate based polyols, methods of makingsuch polycarbonate based polyols, and polyurethane products preparedusing such polycarbonate based polyols.

INTRODUCTION

Polycarbonate based polyols, and efficient methods of preparing suchpolycarbonate based polyols, are of interest in areas including the areaof polyurethanes based polymers. For example, polycarbonate basedpolyols may be poly(ether-carbonate) polyols that are produced usingboth one or more alkylene oxides and carbon dioxide, e.g., to make theresultant polyol cheaper and greener. U.S. Pat. No. 9,080,010, discussesa process for the preparation of polyether carbonate polyols bycatalytic co-polymerization of carbon dioxide with an alkylene oxide inthe presence of one or more H-functional starter substances with the aidof double metal cyanide (DMC) catalysts and in the presence of metalsalts (such as metal halides or metal carboxylates). However, such aprocess disclosed therein may be expensive and require special operatingequipment, e.g., due to high operating pressures. Accordingly,improvements are sought.

SUMMARY

Embodiments may be realized by providing a method of manufacturing apoly(ether-carbonate) polyol comprises a polymerization stage thatincludes polymerizing carbon dioxide and at least one alkylene oxide,with a starter, in the presence of a double metal cyanide polymerizationcatalyst and a catalyst promoter that is devoid of halide anions andcyanide. The catalyst promoter is separate from the double metal cyanidepolymerization catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates and exemplary process flow rate chart for anexemplary method of manufacturing a poly(ether-carbonate) polyol.

DETAILED DESCRIPTION

Polycarbonate based polyols may be prepared using carbon dioxide and/orusing both carbon dioxide and an alkylene oxide (such as propyleneoxide, ethylene oxide, butylene oxide, and/or combinations thereof). Thecarbon dioxide may be at least partially in a gaseous phase (e.g.,because the reaction may occur at relatively low pressures) and thealkylene oxide may be at least in a liquid phase (may include at least aportion in the gas phase, but to an extent less than the carbondioxide). The polycarbonate based polyol according to exemplaryembodiments may be used to prepare a polyurethane product, whichpolyurethane product is prepared using an isocyanate component and anisocyanate-reactive component. For example, the polycarbonate basedpolyol may be included as the only polyol or as one polyol in a blend oftwo or more polyols in the isocyanate-reactive component. Exemplarypolyurethane products include polyurethane foams, polyurethaneelastomers, polyurethane coatings, polyurethane sealants, polyurethaneadhesives, and polyurethane composite materials. According toembodiments, the polycarbonate based polyols are prepared using a doublemetal cyanide (DMC) catalyst and a catalyst promoter, in at least twostages, a preliminary stage and a polymerization stage. The preliminarystage may be used for reactor startup prior to the polymerization stageand/or for adding components not in the presence of polymerizationconditions prior to starting the polymerization stage.

The exemplary embodiments enable the use of the DMC catalyst as thepolymerization catalyst to produce the poly(ether-carbonate) polyolwithout having to rely on specialized polymerization catalyststructures, e.g., the bimetallic catalyst complexes discussed inInternational Publication No. WO 2009/130470 or the catalyst formuladiscussed in International Publication No. WO 2016/012785. For example,in exemplary embodiments, the DMC catalyst may be the solepolymerization catalyst used in the production of thepoly(ether-carbonate) polyol. It is believed the catalyst promoter doesnot directly act as a polymerization catalyst, but acts to enhance theperformance of the DMC polymerization catalyst when forming thepoly(ether-carbonate) polyol.

The exemplary embodiments may avoid the use of a specific polymerizationsystem that includes a specialized catalyst (having a metal complexincluding a permanent ligand set and at least one ligand that is apolymerization initiator) used with a specialized chain transfer agent(having a plurality of sites capable of initiating copolymerization ofepoxides and CO₂), e.g., as discussed in International Publication No.WO 2010/028362. For example, referring to the disclosure in WO2010/028362, the exemplary embodiments may avoid the use of thespecialized chain transfer agent having the structure Y-A-(Y)_(n),where: each —Y group is independently a functional group capable ofinitiating chain growth of epoxide CO₂ copolymers and each Y group maybe the same or different; -A- is a covalent bond or a multivalentmoiety; and n is an integer between 1 and 10, inclusive. Whereas, each Ygroup may be independently selected from the group consisting of: —OH,—C(O)OH, —C(0R^(y))0H, —0C(R^(y))0H, —NHR^(y), —NHC(O)R^(y),—NHC═NR^(y); —NR^(y)C═NH; —NR^(y)C(NR^(y) ₂)═NH; —NHC(NR^(y) ₂)═NR^(y);—NHC(0)0R^(y), —NHC(O)NR^(y) ₂; —C(O)NHR^(y), —C(S)NHR^(y),—OC(O)NHR^(y), —OC(S)NHR^(y), —SH, —C(O)SH, —B(OR^(y))OH,—P(O)_(Ω)(R^(y))_(δ)(OR^(y))_(c)(OX_(l)H,—OP(O)_(Ω)(R^(y))_(δ)(OR^(y))_(c)(O)_(£/)H, —N(R^(y))OH, —ON(R^(y))H,═NOH, ═NN(R^(y))H, where each occurrence of R^(y) is independently —H,or an optionally substituted radical selected from the group consistingof C₁₋₂₀ aliphatic, C₁₋₂₀ heteroaliphatic, 3- to 12-memberedheterocyclic, and 6- to 12-membered aryl, a and b are each independently0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b, and c is 1 or2 and where an acidic hydrogen atom bound in any of the above functionalgroups may be replaced by a metal atom or an organic cation.

With respect to preparing poly(ether-carbonate) polyols, DMC catalyststypically strongly promote the polymerization of propylene oxide, andthus can be used to produce high yield poly(propylene oxide) polyols.The DMC catalysts may also be used in the presence of other alkyleneoxides, such as ethylene oxide and/or butylene oxide. Further, very lowconcentrations of the DMC catalyst complex (e.g., less than 25 ppm ofthe DMC catalyst based on the weight of the product) have in someinstances been found to provide commercially acceptable polymerizationrates, particularly when the polyether product has a hydroxyl equivalentweight of 800 or more. The ability to perform the polymerization usingvery low catalyst levels can lead to a very significant reduction incatalyst costs. However, one problem with DMC catalyst is that theysometimes activate slowly, do not activate at all, or may be inactivatedin the presence of certain materials. For example, the DMC catalysts maybe inactivated in the presence of carbon dioxide. Thus, the stage ofintroducing carbon dioxide into the polyol may result in low yields andsuch poly(ether-carbonate) polyol products may be very difficult toproduce at an industrial scale. Very little or no polymerization occursuntil the catalyst has become activated or after the catalyst has beeninactivated, so such long activation times and inactivation have adirect negative impact on the productivity of the process. What isdesired is an economical and efficient way to produce thesepolycarbonate based polyols.

The preparation of polyethers using the DMC catalyst includes a catalystactivation period. During this period, the DMC catalyst is believed tobecome converted in situ from an inactive form into a highly active formthat rapidly polymerizes the alkylene oxide as long as it remainsactive. This catalyst activation period is typically an indeterminateperiod of time following the first introduction of alkylene oxide (suchas propylene oxide) to the reactor. It is common to introduce a smallamount of alkylene oxide at the start of the polymerization process andthen wait unit the catalyst has become activated (as indicated, e.g., bya drop in reactor pressure due to the consumption of the initialalkylene oxide charge) before continuing with the alkylene oxide feed.

In the polymerization stage, the alkylene oxide and carbon dioxide areadded either in a continuous or step-wise manner, in processes thatoperate either in continuous or semi-batch operation. The preliminarystage may occur in the presence of starter that includes a mono-alcoholinitiator and/or poly-alcohol initiator (such as low molecular weightstarter polyol) and may include heating the catalyst with or without thepresence of the alkylene oxide and/or carbon dioxide. The catalyst maybe activated during the preliminary stage or the polymerization stage,e.g., the catalyst may be activated when propylene oxide is added to thereactor. For example, in semi-batch operations, the catalyst activationstage may occur at least during the preliminary stage, and before thepolymerization stage, and may be performed optionally with or withoutthe presence of carbon dioxide in the reactor. In continuous operations,the catalyst activation may at least occur simultaneously withpolymerization, as new un-activated catalyst, alkylene oxide, carbondioxide, and a starter are introduced continuously into the reactor.During the catalyst activation stage, it is believed the catalyst (suchas DMC catalyst) is converted in situ from an inactive form into ahighly active form that rapidly polymerizes the carbon dioxide andalkylene oxide. According to exemplary embodiments, the polymerizationreaction may be sustained by the un-activated catalyst undergoing theactivation step in the presence of a low molecular weight polyol andalkylene oxide, despite the presence of the carbon dioxide.

For example, during semi-batch or continuous operations, the catalystactivation period may occur at a first temperature and at least aportion of the polymerization stage may be performed at a secondtemperature. The first temperature for catalyst activation may be higheror lower than the second temperature for polymerization reaction. Forexample, the catalyst activation period may occur during the preliminarystage, which includes a heating stage or a cooling stage. The firsttemperature may be equal to or greater than 50° C., than 120° C., and/orthan 150° C. The second temperature may be equal to or greater than 50°C. Both the first temperature and the second temperature may be lessthan 165° C. For example, the second temperature may be within the rangefrom 50° C. to 165° C. (e.g., from 65° C. to 155° C., from 80° C. to150° C., and/or from 90° C. to 140° C.). The difference between thefirst temperature and the second temperature may be at least 10° C., atleast 20° C., at least 30° C., at least 40° C., and/or at least 50° C.Optionally, the first temperature and the second temperature may be thesame temperature.

According to exemplary embodiments, the formation of polycarbonate basedpolyols may be observed in the presence of the DMC catalysts and thecatalyst promoter, under mild operating conditions. Exemplary DMCcatalysts include zinc hexacyanocobaltate catalyst complexes. Forexample, by mild operation conditions it is meant that the process maybe performed in conventional low pressure polyol production equipment,such that specialized equipment for high pressure and/or hightemperature operations may not be required. For example, polycarbonatebased polyols having a carbonate content from 0.1 wt % to 25 wt % can beprepared in conventional reactors and at high reaction rates with highselectivity, using the process according to exemplary embodiments.

Exemplary pressure operation conditions, for at least one of the stagesand/or in all of the stages, for forming the polycarbonate based polyolinclude pressures that range from 40 psig to 750 psig (e.g., from 80psig to 150 psig and/or from 100 psig to 140 psig). Other exemplarypressures include from 0.4 MPa to 5.3 MPa (e.g., from 0.7 MPa to 1.1 MPaand/or from 0.8 MPa to 0.9 MPa). During the catalyst activation stagethe pressure may range from 0 psig before alkylene oxide addition, up to750 psig. Under continuous operating conditions the reactor pressure isheld constant at a fixed operating process control pressure usuallycorresponding to pressures between 20 psig and 150 psig.

The resultant polycarbonate based polyols, such as poly(ether-carbonate)polyols, may have a nominal hydroxyl functionality from 2 to 8 (e.g.,from 2 to 6 and/or from 2 to 4). The polycarbonate based polyols, suchas poly(ether-carbonate) polyols, may have a hydroxyl equivalent weightof from 150 to 4000 g/mol equivalence (e.g., from 200 to 2000 g/molequivalence and/or from 500 to 1500 g/mol equivalence).

Process Stages

The polyol may be prepared using a batch, semi-batch, and/or continuousprocess. For example, a semi-batch type process or a continuous additionof starter (i.e., CAOS) type process may be used. DMC is regarded as amore efficient catalyst, e.g., as compared to KOH. Use of the DMCcatalyst may allow for the addition of low molecular weight starters tohigh molecular weight carrier polyols, significantly reduces by-productformation and lowers volatile organic compound formation (low VOCs), andprovides a reduction in total energy consumption.

The polymerization stage in the process of forming the polycarbonatebased polyols may be performed in the presence of the DMC catalyst andthe catalyst promoter, and may exclude any other polyol polymerizationcatalysts such as potassium hydroxide. This is industrially favorable,e.g., because an important advantage of using DMC catalysts additionallywith a catalyst promoter is that the catalyst residues can be left inthe product (e.g., because it is present in very low concentrations ascompared to other catalyst such as potassium hydroxide). This avoids acostly step of neutralizing and removing a polymerization catalyst suchas potassium hydroxide. The polymerization stage includes continuedexposure of the reaction mixture to polymerization conditions in thepresence of the DMC catalyst and the catalyst promoter to polymerizemost or all of the remaining oxides. The amount of unreacted oxides maybe reduced in this step to, e.g., less than 2 wt %, less than 1 wt %,and/or less than 0.5 wt %, based on an aggregate weight of the one ormore co-feed mixtures.

During the polymerization stage, carbon dioxide and/or an alkylene oxideare fed into the reaction, and optionally the catalyst and/or catalystpromoter may also be added. The carbon dioxide and alkylene oxide may befed together or may be fed separately. For example, a mixed feed ofcarbon dioxide and alkylene oxide may be fed into the reactionintermittently (e.g., at predetermined intervals) or continuously (e.g.,over a predetermined amount of time) during the polymerization stage. Inanother example, the carbon dioxide may be fed into the reactorintermittently (e.g., at predetermined intervals) or continuously (e.g.,over a predetermined amount of time). Further, independently, thealkylene oxide in a separate feed may be added into the reactionintermittently (e.g., at predetermined intervals) or continuously (e.g.,over a predetermined amount of time) during the polymerization stage. Inan exemplary embodiment, the carbon dioxide may be fed into a reactorintermittently (e.g., at predetermined intervals based on reactorpressure) and the alkylene oxide (such as propylene oxide) may be feedinto the reactor continuously. The addition of carbon dioxide may becontinued after the addition of alkylene oxide has ceased, or optionallythe addition of alkylene oxide may be continued after the addition ofcarbon dioxide has ceased. Thereafter, the resulting reaction forms thepoly(ether-carbonate) polyol having a backbone that includes both ethergroups and carbonate groups. The poly(ether-carbonate) polyol mayinclude primary hydroxyl groups and/or secondary hydroxyl groups.

The polymerization stage may include more than one digestion stage, forwhich between each digestion stage a different or same feed rate for thecarbon dioxide and/or alkylene oxide relative to another digestion stagemay be used. In an exemplary embodiment, each digestion stage may startafter the addition of the carbon dioxide and/or alkylene oxide hasstopped, such that the reaction mixture is digested during the stage. Inan exemplary embodiment, one or more digestion stages may include acontinuous feed of alkylene oxide, and an intermittent feed of carbondioxide prior to each digestion stage. For example, the intermittentfeed may be varied, such that a higher feed rate of carbon dioxide maybe used prior to the first continuous digestion stage and a relativelylower feed rate prior to a subsequent digestion stage, or a lower feedrate of carbon dioxide may be used for the first continuous digestionstage and a relatively higher feed rate during a subsequent digestionstage.

The carbon dioxide and/or an alkylene oxide (separately or as a co-feedmixture) may be added continuously or intermittently during thepolymerization stage, under polymerization conditions, to controlinternal reactor pressures and to control the level of unreacted oxidesin the reaction vessel to a reasonable level. For example, the carbondioxide may be fed on demand during the polymerization stage, byintroducing the carbon dioxide as it is consumed, to produce a constantreactor pressure during this stage. Each intermittent addition of carbondioxide may correspond to the start of a digestion stage, such that asthe feed of carbon dioxide is stopped the digestion stage begins. Insuch an exemplary embodiment, the alkylene oxide may be feed into thereactor at a continuous feed rate, such that a decrease in reactorpressure can be attributed to consumption of the carbon dioxide.

The addition of alkylene oxide to the process may be a single alkyleneoxide, a mixture of alkylene oxides, or a feed of a single oxide ormixture of oxides during part of the semi-batch process followed by afeed of a different single oxide or a different mixture of oxides duringa different phase of the process. In this manner any combination ofsingle or multiple alkylene oxides may be added to the semi-batchprocess.

For example, a co-feed mixture of carbon dioxide and alkylene oxideincludes 0.5 wt % to 43.0 wt % of carbon dioxide and 57.0 wt % to 99.5wt % of the alkylene oxide (based on a total weight of the co-feedmixture or said in another way based on the total weight of carbondioxide and alkylene oxide used to form the polyol), which ispolymerized in the presence of the catalyst, catalyst promoter, and thestarter. In exemplary embodiment, the amount of incorporation of thecarbon dioxide into the poly(ether-carbonate) polyol may be from 1 wt %to 30 wt %, 1 wt % to 25 wt %, 1 wt % to 20 wt %, 1 wt % to 15 wt %, 2wt % to 15 wt %, 3 wt % to 15 wt %, 3 wt % to 12 wt %, etc., which theremainder being the alkylene oxide.

In exemplary embodiments, the alkylene oxide contains 86 to 100% byweight 1,2-propylene oxide, 0 to 12% by weight ethylene oxide and 0 to2% by weight of other copolymerizable monomers). For example, the amountof the carbon dioxide relative to alkylene oxide may be different and/orthe alkylene oxide used may be different. During the polymerizationstage, the respective co-feed mixture is introduced to the reactionunder polymerization conditions, whereas co-feed mixture is fedcontinuously or intermittently and/or at an increasing rate, decreasingrate, or constant rate over a period of time. In exemplary embodiments,the co-feed mixture includes a majority of the alkylene oxide (e.g., atleast 50 wt %, at least 60 wt %, at least 70 wt %, at least 75 wt %, atleast 79 wt %, etc.), with the remainder being the carbon dioxide. Forexample, the molar ratio in the co-feed mixture of the carbon dioxide toalkylene oxide may be from 1:1 to less than 1:200 (e.g., from 1:1 to1:100, from 1:8 to 1:17, from 1.0:1.3 to 1.0:9.0, etc.).

According to an exemplary embodiment using a semi-batch polymerizationmethod, after the preliminary stage, at least the carbon dioxide andalkylene oxide are charged to a reaction vessel, in the presence of theDMC catalyst, catalyst promoter, and starter, and then heated to thesecond temperature (i.e., the polymerization temperature) until thedesired molecular weight is obtained. One way of performing a batchpolymerization is to combine the DMC catalyst, catalyst promoter, andstarter (optionally in the presence of a polyether having a hydroxylequivalent weight up to that of the product of the polymerization) atthe first temperature during the preliminary stage. Then, the carbondioxide and/or alkylene oxide are added and the resulting mixture issubjected to polymerization conditions. Additional DMC catalyst and/orcatalyst promoter may be added during the course of the carbon dioxideand/or alkylene oxide addition.

In an exemplary semi-batch process, before, after, or during thepolymerization stage, the DMC catalyst, catalyst promoter, and starterare combined. A portion of the carbon dioxide and alkylene oxide areintroduced into the reaction vessel (e.g., independently continuously orintermittently) and the contents of the vessel are heated (if necessary)to the polymerization temperature. When the DMC catalyst has becomeactivated (typically as indicated by a drop of internal reactorpressure), more carbon dioxide and/or alkylene oxide may be fed to thereactor under polymerization conditions. The feed of the carbon dioxideand/or alkylene oxide is continued until enough has been consumed toreach the target product molecular weight. Additional DMC catalystand/or catalyst promoter may be added during the course of the carbondioxide and/or alkylene oxide addition. In the semi-batch process, theentire amount of starter used may be added at the start of the process,or optionally can be added during the polymerization stage. After thefeed is completed, the remaining carbon dioxide may be vented off.Optionally, the reaction mixture may be cooked down at thepolymerization temperature in an attempt to consume at least some of theremaining alkylene oxide and/or carbon dioxide. For example, the batchand semi-batch processes may be suitable for producing apoly(ether-carbonate) polyol having a hydroxyl equivalent weight of upto 1000, from a starter having a hydroxyl equivalent weight of from 30to 150. The batch and semi-batch processes may also be used to makepolyethers having higher equivalent weights. The poly(ether-carbonate)polyol may be a diol or triol.

In an exemplary continuous polymerization process, during thepolymerization stage, there may be continuous addition of the carbondioxide and/or alkylene oxide, and continuous removal of product. Forexample, the feed of the alkylene oxide may be continuous, while thecarbon dioxide is fed intermittently. A continuous process is generallyconducted by establishing steady-state concentrations, within theoperational capabilities of the polymerization equipment, of the DMCcatalyst, catalyst promoter, starter, carbon dioxide, and alkylene oxideand polymerizate under polymerization conditions in a continuous reactorsuch as a loop reactor, a tubular or plug-flow reactor or a continuousstirred tank reactor. The “polymerizate” is a mixture of polyethersand/or poly (ethers-carbonates) that have molecular weights greater thanthat of the starter and up to that of the intended product. AdditionalDMC catalyst, catalyst promoter, starter, carbon dioxide, and/oralkylene oxide may be continuously added to the reactor, e.g., as asingle stream, as separate components, or in various sub-combinations. Aproduct stream is continuously withdrawn from the reactor. The rates ofthe additional stream(s) and product streams are selected to maintainsteady-state conditions in the reactor (within the capabilities of theequipment), and to produce a product having a desired molecular weight.The product stream withdrawn from the continuous reactor may be cookeddown for some period of time to allow the unreacted alkylene oxide inthat stream to be consumed to low levels. For example, continuousprocess may be particularly suitable for producing apoly(ether-carbonate) product having a hydroxyl equivalent weight from150 to 5000 (e.g., from 350 to 2500 and/or from 500 to 2000). Thepoly(ether-carbonate) product may be a diol or triol.

At the start-up of a continuous process, a mixture formed by combiningthe DMC catalyst, the catalyst promoter, and an initial polymerizationstarter optionally in the presence of carbon dioxide may be subjected toa preliminary heating step as described before, before being contactedwith the alkylene oxide (e.g., during the preliminary stage). In acontinuous process, the initial polymerization starter can be a lowermolecular weight, a higher molecular weight, or the same molecularweight as the final product. The starter can optionally be identical incomposition to the intended final product.

The polymerization reaction can be performed in any type of vessel thatis suitable for the pressures and temperatures encountered. In acontinuous or semi-continuous process, the vessel should have one ormore inlets through which the carbon dioxide and alkylene oxide andadditional starter compound can be introduced during the reaction. In acontinuous process, the reactor vessel may contain at least one outletthrough which a portion of the partially polymerized reaction mixturecan be withdrawn. A tubular reactor that has one or multiple points forinjecting the starting materials, a loop reactor, and a continuousstirred tank reactor (CTSR) are all suitable types of vessels forcontinuous or semi-batch operations. The reactor should be equipped witha means of providing or removing heat, so the temperature of thereaction mixture can be maintained within the required range. Suitablemeans include various types of jacketing for thermal fluids, varioustypes of internal or external heaters, and the like. A cook-down stepperformed on continuously withdrawn product is conveniently conducted ina reactor that reduces the possibility of and/or prevents significantback-mixing from occurring. Plug-flow operation in a pipe or tubularreactor is an exemplary manner of performing such a cook-down step.

The product obtained in any of the foregoing processes may contain up to0.5 wt %, based on the total weight, of unreacted carbon dioxide and/oralkylene oxide, small quantities of the starter and low molecular weightalkoxylates thereof, and small quantities of other organic impuritiesand water. Volatile impurities should be flashed or stripped from theresultant product. The product typically contains catalyst residues andresidues of the catalyst promoter. It is typical to leave these residuesin the product, but these can be removed if desired. Moisture andvolatiles can be removed by stripping the polyol.

A process of producing the poly(ether-carbonate) polyol includespolymerizing the carbon dioxide and at least one alkylene oxide, withthe starter, in the presence of the DMC catalyst and the catalystpromoter. For example, the method includes the stages of combining theDMC catalyst, the catalyst promoter, the starter, and optionally arelatively small amount of the alkylene oxide (to activate the DMCcatalyst) to form a starting reaction mixture. Then, the startingreaction mixture is heated or cooled to polymerization conditions andthe carbon dioxide and a large amount of the alkylene oxide (as neededfor the polymerization reaction) are added to the starting reactionmixture. Additional amounts of the DMC catalyst complex, the catalystpromoter, and/or starter may be added to the reactor during the time thecarbon dioxide and at least one alkylene oxide are feed.

The carbon dioxide and/or alkylene oxide may be continuously added orintermittently added. In exemplary embodiments, the addition of thecarbon dioxide and optionally that of the alkylene oxide may be based onpressure in the reactor. For example, the carbon dioxide may be added inan amount sufficient to increase the pressure in the reactor to a firstpredetermined pressure that is greater than 60 psig (e.g., greater than0.41 MPa) and less than 200 psig (e.g., 1.38 MPa). Other exemplarypressures include greater than 100 psig, less than 150 psig, less than125 psig, etc. Once the first predetermined pressure is reached, thefeed of the carbon dioxide may be stopped to allow for a digestion stageto occur thereafter. Once the pressure in the reaction reaches a secondpredetermined pressure, which is lower than the first predeterminedpressure, additional carbon dioxide may be added to perform anadditional digestion stage and/or the addition of any additionalmaterials (if any) may by stopped to allow for completion of thepolymerization stage (e.g., after one more digestion stage). The secondpredetermined pressure may be less than the first predetermined pressureby an amount such as 5 psig (e.g., 0.03 MPa), 10 psig (e.g., 0.07 MPa),15 psig (e.g., 0.10 MPa), 20 psig (e.g., 0.14 MPa), 25 psig (e.g., 0.17MPa), 30 psig (e.g., 0.20 MPa) etc.

An exemplary method of producing the poly(ether-carbonate) polyolincludes (a) establishing steady-state concentrations of (i) the DMCcatalyst, (ii) the catalyst promoter, (iii) the starter, (iv) the carbondioxide, (v) the alkylene oxide, and (vi) the polymerizate in acontinuous reactor under polymerization conditions; and (b) continuouslyadding additional starter, alkylene oxide, DMC catalyst, and catalystpromoter, to the continuous reactor under polymerization conditions andcontinuously withdrawing a product stream containingpoly(ether-carbonate) polyol from the continuous reactor. An exemplarysemi-batch process may include adding the starter, DMC catalyst, andcatalyst promoter to the reactor, adding an initial charge of alkyleneoxide to the reactor to activate the catalyst, then co-feeding thecarbon dioxide and the alkylene oxide to the reactor underpolymerization conditions. Optionally, the carbon dioxide can be addedto the reactor in any proportion before the initial charge of alkyleneoxide which is used to activate the catalyst.

The method of producing the poly(ether-carbonate) polyol may includecombining the DMC catalyst and the catalyst promoter with an alkyleneoxide and at least one initiator compound to form a starting reactionmixture, and then heating the starting reaction mixture topolymerization conditions until the double metal cyanide catalystcomplex becomes activated and then feeding additional alkylene oxide andthe carbon dioxide to the starting reaction mixture under polymerizationconditions. In exemplary embodiments, a preliminary stage may include,adding carbon dioxide and subsequently venting the added carbon dioxide,in order to prepare the reactor for the polymerization stage.

During the preliminary stage, a preliminary heating step may beperformed by heating the DMC catalyst and catalyst promoter to atemperature of from 80° C. to 220° C. at atmospheric or sub-atmosphericpressure for a period of 10 minutes or more prior to adding the carbondioxide and alkylene oxide.

Starter

The starter may include a mono-alcohol initiator and/or a poly-alcoholinitiator (such as a low molecular weight starter polyether polyol). Itis possible to perform the polymerization in the presence of a starterthat includes a mixture of the mono-alcohol initiator and low molecularweight starter polyol. The result of such a polymerization may be apoly(ether-carbonate) mixture containing monols and polyols.

The mono-alcohol initiator may have a hydroxyl equivalent weight of from30 to 1000. The poly-alcohol initiator may have a hydroxyl equivalentweight of 3,000 g/mol or less (e.g., 1,500 g/mol or less).

For example, the mono-alcohol initiator may have at least one aliphaticcarbon-carbon double bond, said carbon dioxide and alkylene oxide beingpolymerized onto starter during the one or more digestion stages. Thecarbon-carbon double bond may be, e.g., vinyl (CH₂═CH—), allylic(CH₂═CH—CH₂—) or propenyl (CH₃—CH═CH₂—) unsaturation. The unsaturatedmonoalcohol may contain, for example, up to 30 carbon atoms, up to 20carbon atoms or up to 12 carbon atoms. Examples of unsaturated alcoholsinclude vinyl alcohol, 1-propen-3-ol, 1-buten-4-ol, 1-hexen-6-ol,1-heptene-7-ol, 1-octen-8-ol, 1-nonen-9-ol, 1-decen-10-ol,1-undecen-11-ol, 1-dodecen-12-ol, allyl alcohol, hydroxyethylacrylate,hydroxypropylacrylate, hydroethylmethacrylate, and the like, as well asalkoxylates of any of the foregoing having molecular weights of up to1000 (e.g., up to 500). Any two or more of the foregoing may be used.

Exemplary poly-alcohol starters include ethylene glycol, diethyleneglycol, triethylene glycol, propylene glycol, dipropylene glycol,tripropylene glycol, glycerin, trimethylolpropane, pentaerythritol,sucrose, sorbitol, and alkoxylates, of any combinations thereof having ahydroxyl equivalent weight of up to 1000.

Low molecular weight polyol starters includes two or more hydroxylgroups, and exemplary starters include polyols alkoxylated with ethyleneoxide, propylene oxide and/or butylene oxide in any relative proportion.At least one other reactive oxirane may also be used singularly orincluded along with the more standard oxiranes list above, such asstyrene oxide, epichlorohydrin, octene oxide, and allyl glycidyl ether.

The polymerization reaction for forming poly(ether-carbonate) polyol maybe characterized by the “build ratio”, which is defined as the ratio ofthe number average molecular weight of the polyether product to that ofthe starter. This build ratio may be as high as 160. Exemplaryembodiments include a range from 2 to about 65 (e.g., 2 to 50, 2 to 15,7 to 11, etc.) For example, during the polymerization stage, the startermay constitutes 0.5 wt % to 90.0 wt % of the weight of thepoly(ether-carbonate) polyol forming mixture.

Catalyst

The polymerization catalyst is a double metal cyanide catalyst complex,also referred to herein as DMC catalyst. Exemplary DMC catalysts includethose described, e.g., in U.S. Pat. Nos. 3,278,457; 3,278,458;3,278,459; 3,404,109; 3,427,256; 3,427,334; 3,427,335; and 5,470,813.

Exemplary DMC catalysts can be represented by the Formula 1:

M_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d) .nM³ _(x)A_(y)  Formula 1

wherein M and M³ are each metals; M¹ is a transition metal differentfrom M, each X represents a group other than cyanide that coordinateswith the M¹ ion; M² is a transition metal; A represents an anion; b, cand d are numbers that reflect an electrostatically neutral complex; ris from 4 to 6; t is from 0 to 2; x and y are integers that balance thecharges in the metal salt M³ _(x)A_(y), and n is zero or a positiveinteger. The foregoing formula does not reflect the presence of neutralcomplexing agents such as t-butanol which are often present in the DMCcatalyst complex. In exemplary embodiments, r is 4 or 6, t is 0. In someinstances, r+t will equal six.

For example, NI and M³ may each be a metal ion independently selectedfrom the group of Zn²⁺, Fe²⁺, Co⁺²⁺, Ni²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺,Sr²⁺, W⁴⁺, W⁶⁺, Mn²⁺, Sn²⁺, Sn⁴⁺, Pb²⁺, Cu²⁺, La³⁺ and Cr³⁺. M¹ and M²may each be selected from the group of Fe³⁺, Fe³⁺, Fe²⁺, Co³⁺, Co²⁺,Cr²⁺, Cr³⁺, Mn²⁺, Mn³⁺, Ir³⁺, Ni²⁺, Rh³⁺, Ru²⁺, V⁴⁺, V⁵⁺, Ni²⁺, Pd²⁺,and Pt²⁺. Among the foregoing, those in the plus-three oxidation statemay be used as the M¹ and M² metal (e.g., Co⁺³ and Fe⁺). Suitable anionsA include, but are not limited, to halides such as chloride, bromide andiodide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate,isocyanate, perchlorate, isothiocyanate, an alkanesulfonate such asmethanesulfonate, an arylenesulfonate such as p-toluenesulfonate,trifluoromethanesulfonate (triflate) and a C₁₋₄ carboxylate.

An exemplary type of DMC catalyst is a zinc hexacyanocolbaltatecomplexed with t-butanol.

According to exemplary embodiments, the DMC catalyst performs in thepresence of carbon dioxide and/or when the concentration of hydroxylgroups is high during the digestion/polymerization process, activatingrapidly and providing good polymerization rates without deactivatingprematurely. The process of manufacturing using the DMC catalyst isamenable to the production of such polycarbonate polyols, such aspoly(ether-carbonate polyols) having hydroxyl equivalent weights of from150 to 5,000 or more. In addition, the process provides a method bywhich the carbon dioxide and/or alkylene oxide can be polymerized onto alow equivalent weight starter such as propylene glycol, glycerin,trimethylol propane, sorbitol, sucrose, low molecular weight alkoxylatesof these initiators, or combinations thereof.

Promoter

Catalyst deactivation (such as for the DMC catalyst) may occur in thepresence of high concentration of hydroxyl groups. For example,alkoxylation of initiators may not easily proceed directly from a lowmolecular weight mono-alcohol or poly alcohol initiator to the finishedpolyol, because the high concentration of hydroxyl groups and initiatorcompound during early stages of the polymerization may severely inhibitinitial catalyst activation. Therefore, it is proposed to produce thepolycarbonate based polyol, comprising polymerizing of carbon dioxideand at least one alkylene oxide in the presence of the DMC catalyst (asthe polymerization catalyst) and a catalyst promoter. The catalystpromoter is separate from the DMC catalyst, e.g., is not a ligand on acatalyst and may be separately added to a reaction mixture. In exemplaryembodiments, the catalyst promoter may be devoid of halide anions. Thecatalyst promoter may be devoid of cyanide. In exemplary embodiments,the catalyst promoter may be devoid of any organic phenols, such asphenols that do not additionally include a magnesium, a Group 3-Group 15metal, or a lanthanide series compound. In exemplary embodiments, thecatalyst promoter may be devoid of zinc ions, such that the catalystpromoter includes a Group 3-Group 15 metal, other than zinc.

For example, the catalyst promoter is a magnesium, a Group 3-Group 15metal, or a lanthanide series compound in which the magnesium, Group3-Group 15 metal, or lanthanide series metal is bonded to at least onealkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate,thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester,amide, siloxide, hydride, carbamate or hydrocarbon anion, and whereinthe magnesium, Group 3-Group 15, or lanthanide series metal compound isdevoid of halide anions. Exemplary promoters are discussed in U.S. Pat.No. 9,040,657. In exemplary embodiments, use of Group 3-Group 15 metal,or lanthanide series metal bonded to a carboxylate may be avoided.

With use of the catalyst promoter, an exemplary method for producing thepolycarbonate based polyol includes, prior to and/or during at least oneof the one or more digestion/polymerization stages, the following (1)forming a catalyst mixture by combining (a) the DMC catalyst and (b) thecatalyst promoter, which is the magnesium, Group 3-Group 15 metal, orlanthanide series metal compound in which the magnesium, Group 3-Group15 metal, or lanthanide series metal compound is bonded to at least onealkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate,thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester,amide, siloxide, hydride, carbamate or hydrocarbon anion, and whereinthe magnesium, Group 3-Group 15 metal, or lanthanide series metalcompound is devoid of halide anions; (2) combining the catalyst mixturewith a feed that includes carbon dioxide and/or an alkylene oxide; and(3) polymerizing the carbon dioxide and/or alkylene oxide.

An exemplary method of producing the polycarbonate based polyol, such asthe poly(ether-carbonate) polyol, includes polymerizing both carbondioxide and the alkylene oxide in the presence of the DMC catalyst and amagnesium, Group 3-Group 15 metal, or lanthanide series compound inwhich the magnesium, Group 3-Group 15 metal, or lanthanide series metalis bonded to at least one alkoxide, aryloxy, carboxylate, acyl,pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphateester, thiophosphate ester, amide, siloxide, hydride, carbamate orhydrocarbon anion, and wherein the magnesium, Group 3-Group 15, orlanthanide series metal compound is devoid of halide anions.

In exemplary embodiments, it is believed the presence of the catalystpromoter, e.g., magnesium, Group 3-Group 15 metal, or lanthanide seriesmetal compound (sometimes referred to herein as “MG3-15LA compound”) maysignificantly reduce the time required to activate the DMC catalyst,compared to when the DMC catalyst is used by itself (e.g., when theMG3-15LA compound is absent). After the DMC catalyst has becomeactivated, faster polymerization rates may be seen, compared to when theDMC catalyst is used by itself (e.g., when the MG3-15LA compound isabsent). Also, certain promoter metals appear to provide especially fastpolymerization rates.

The catalyst promoter, e.g., MG3-15LA compound, is a separately addedingredient, which is not present during the preparation (i.e., theprecipitation step) of the DMC catalyst. The MG3-15LA compound containsa magnesium, Group 3-Group 15 metal, or lanthanide series metal ionbonded to at least one alkoxide, aryloxy, carboxylate, acyl,pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphateester, thiophosphate ester, amide, siloxide, hydride, carbamate orhydrocarbon anion. The catalyst promoter is devoid of halide anions. Thecatalyst promoter is devoid of cyanide.

By alkoxide anion it is meant a species having the form ⁻O—R, where R isan alkyl group or substituted alkyl group, and which is the conjugatebase, after removal of a hydroxyl hydrogen, of an alcohol compoundhaving the form HO—R. These alcohols typically have pKa values in therange of 13 to 25 or greater. The alkoxide ion may contain from 1 to 20(e.g., from 1 to 6 and/or from 2 to 6) carbon atoms. The alkyl group orsubstituted alkyl group may be linear, branched, and/or cyclic. Examplesof suitable substituents include, e.g., additional hydroxyl groups(which may be in the alkoxide form), ether groups, carbonyl groups,ester groups, urethane groups, carbonate groups, silyl groups, aromaticgroups (such as phenyl and alkyl-substituted phenyl), and halogen.Examples of such alkoxide ions include methoxide, ethoxide,isopropoxide, n-propoxide, n-butoxide, sec-butoxide, t-butoxide,benzyloxy, and the like. In other embodiments, the R group may containone or more hydroxyl groups and/or may contain one or more etherlinkages. An alkoxide ion may correspond to the residue (after removalof one or more hydroxyl hydrogens) of an initiator compound that ispresent in the polymerization, such as those initiator compoundsdescribed below. The alkoxide ion may be an alkoxide formed by removingone or more hydroxyl hydrogens from a polyether monol or polyetherpolyol.

By aryloxy anion it is meant a species having the form —O—Ar, where Aris an aromatic group or substituted group, and which corresponds, afterremoval of a hydroxyl hydrogen, to a phenolic compound having the formHO—Ar. These phenolic compounds may have a pKa of, e.g., from 9 to 12.Examples of such aryloxy anions include phenoxide and ring-substitutedphenoxides, whereas the ring-substituents include, e.g., alkyl, CF₃,cyano, CH₃, COCH₃, halogen, hydroxyl, alkyl, alkoxyl, and the like. Thering-substituent(s), if present, may be in one or more of the ortho-,para- and/or meta-positions relative to the phenolic group. Thephenoxide anions also include the conjugate bases of polyphenoliccompounds such as bisphenol A, bisphenol F and various other bisphenols,1,1,1-tris(hydroxyphenyl)ethane, and fused ring aromatics such as1-naphthol and the like.

By carboxylate anion it is meant a carboxylate having from 1 to 24(e.g., from 2 to 18 and/or from 2 to 12) carbon atoms. It may bealiphatic or aromatic. An aliphatic carboxylic acid may containsubstituent groups such as hydroxyl groups (which may be in the alkoxideform), ether groups, carbonyl groups, ester groups, urethane groups,carbonate groups, silyl groups, aromatic groups such as phenyl andalkyl-substituted phenyl, halogen, and the like. Examples of aliphaticcarboxylate anions include formate, acetate, propionate, butyrate,2-ethylhexanoate, n-octoate, decanoate, laurate and other alkanoates andhalogen-substituted alkanoates such as 2,2,2-trifluoroacetate,2-fluoroacetate, 2,2-difluoroacetate, 2-chloroacetate,2,2,2-trichloroacetate and the like. Aromatic carboxylates includebenzoate, alkyl-substituted benzoate, halo-substituted benzoate,4-cyanobenzoate, 4-trifluoromethylbenzoate, salicylate,3,5-di-t-butylsalicylate, subsalicylate, and the like. In someembodiments, such a carboxylate ion may be the conjugate base of acarboxylic acid having a pKa from 1 to 6 (e.g., from 3 to 5).

By acyl anion, it is meant a conjugate base of a compound containing acarbonyl group including, e.g., an aldehyde, ketone, carbonate, ester orsimilar compound that has an enol form. Among these are β-diketocompounds, such as acetoacetonate, butylacetoacetonate and the like.

Phosphate ester anions include those having the formula —O—P(O)(OR¹)₂,wherein R is alkyl, substituted alkyl, phenyl or substituted phenyl.Thiophosphate esters have the corresponding structure in which one ormore of the oxygens are replaced with sulfur.

By amide anion, it is meant an ion in which a nitrogen atom bears anegative charge. The amide ion generally takes the form —N(R²)₂, whereinthe R² groups are independently hydrogen, alkyl, aryl, trialkylsilyl,triarylsilyl, and the like. The alkyl groups may be linear, branched orcyclic. Any of these groups may contain substituents such as ether orhydroxyl. The two R² groups may together form a ring structure, whichring structure may be unsaturated and/or contain one or more heteroatoms(in addition to the amide nitrogen) in the ring.

Hydrocarbyl anions include aliphatic, cycloaliphatic, and/or aromaticanions, whereas the negative charge resides on a carbon atom. Thehydrocarbyl anions are conjugate bases of hydrocarbons that typicallyhave pKa values in excess of 30. The hydrocarbyl anions may also containinert substituents. For example, of the aromatic hydrocarbyl anions,phenyl groups, and substituted phenyl groups may be used. Aliphatichydrocarbyl anions may be alkyl groups (e.g., containing from 1 to 12and/or from 2 to 8 carbon atoms). Methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, cyclopentadienyl, and t-butyl anions maybe useful.

In exemplary embodiments, the anions are the conjugate base of acompound having a pKa of at least 1.5 (e.g., at least 2.5 and/or atleast 3.0). For example, shorter activation times may be seen when theanions correspond to the conjugate base of a compound having a pKa of atleast 9 (e.g., at least 12 and/or at least 13). The anion may be theconjugate base of a compound having any higher pKa, such as up to 60 orhigher. Anions corresponding to the conjugate base of a compound havinga pKa of less than 9 (e.g., less than 5), may lead to longer activationtimes. Exemplary anions that may be used are alkoxide, aryloxy, amide,acetylacetonate, and hydrocarbyl anions, which are the conjugate base ofa compound having a pKa of at least 9 (e.g., at least 12, at least 13,and/or up to 60).

The Group 3-Group 15 metals are metals falling within any of Groups IIIthrough 15, inclusive, of the 2010 IUPAC periodic table of the elements.The metal may be, e.g., scandium, yttrium, lanthanum, titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium,iridium, nickel, palladium, platinum, copper, silver, gold, zinc,cadmium, mercury, aluminum, gallium, indium, tellurium, germanium, tin,lead, antimony, bismuth, and the lanthanide series metals includingthose having atomic numbers from 58 (cerium) to 71 (lutetium),inclusive. Exemplary metals that may be used include those in Groups 3,4, 5, 12, 13 and 14. Among these, scandium, yttrium, hafnium, titanium,zirconium, niobium, vanadium, zinc, aluminum, gallium, indium and tinare usable in exemplary embodiments, as these metals may tend to providefast polymerization rates and/or allow very small quantities of the DMCcatalyst to be present. For example, Aluminum, zinc, hafnium, gallium,indium, tin, titanium and/or zirconium may be used.

Exemplary promoters are compounds corresponding to either of the formulaM⁴A¹ _(z) and M⁴(O)A¹ _(z), wherein M⁴ is the magnesium, Group 3-Group15, or lanthanide series metal and each A¹ is independently an anion asdescribed before and z is a number of at least one which reflects anelectrostatically neutral compound, provided that any two or more A¹groups may together form a polyvalent group. Each A¹=is independently analkoxide, aryloxy anion, amide anion or hydrocarbyl anion that is theconjugate base of a compound having a pKa of at least 9 (e.g., at least12 and/or at least 13). Any A¹ may be an alkoxide anion, which is theconjugate base of an initiator compound or a polyether monol orpolyether polyol, including the polyether monol or polyether polyolproduct that is obtained from the alkoxylation reaction or a polyetherhaving a molecular weight intermediate to that of the initiator compoundand the product of the alkoxylation reaction.

The promoter compound may be devoid of anions that are conjugate basesof inorganic acids such as sulfate, sulfite, persulfate, nitrate,nitrite, chlorate, perchlorate, hypochlorite, carbonate, chromate, andthe like; sulfonate anions such as trifluoromethylsulfonate and methylsulfonate; and hydroxide ions.

Examples of promoters include:

a) magnesium alkyls such as diethyl magnesium, dibutyl magnesium,butylethyl magnesium, dibenzyl magnesium and the like; magnesiumalkoxides such as magnesium methoxide, magnesium ethoxide, magnesiumisopropoxide, magnesium t-butoxide, magnesium sec-butoxide and the like;magnesium aryloxides such as magnesium phenoxide, and magnesiumphenoxides in which one or more of the phenoxide groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like; magnesium carboxylates such as magnesium formate,magnesium acetate, magnesium propionate, magnesium 2-ethylhexanoate,magnesium benzoate, magnesium benzoates in which one or more of thebenzoate groups is ring-substituted with alkyl, CF₃, cyano, COCH₃,halogen, hydroxyl, alkoxyl and the like, magnesium salicylate, magnesium3,5-di-t-butyl salicylate; magnesium amides such as magnesiumdimethylamide, magnesium diethylamide, magnesium diphenylamide,magnesium bis(trimethylsilyl)amide and the like; magnesiumacetylacetonate and magnesium t-butylacetylacetonate.

b) scandium alkoxides such as scandium methoxide, scandium ethoxide,scandium isopropoxide, scandium t-butoxide, scandium sec-butoxide andthe like; scandium aryloxides such as scandium phenoxide and scandiumphenoxides in which one or more of the phenoxide groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like; scandium carboxylates such as scandium formate,scandium acetate, scandium propionate, scandium 2-ethylhexanoate,scandium benzoate, scandium benzoates in which one or more of thebenzoate groups is ring-substituted with alkyl, CF₃, cyano, COCH₃,halogen, hydroxyl, alkoxyl and the like; scandium salicylate; scandiumacetylacetonate and scandium t-butylacetylacetonate.

c) yttrium alkoxides such as yttrium methoxide, yttrium ethoxide,yttrium isopropoxide, yttrium t-butoxide, yttrium sec-butoxide and thelike; yttrium aryloxides such as yttrium phenoxide, and yttriumphenoxides in which one or more of the phenoxide groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like; yttrium carboxylates such as yttrium formate,yttrium acetate, yttrium propionate, yttrium 2-ethylhexanoate, yttriumbenzoate, yttrium benzoates in which one or more of the benzoate groupsis ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like, yttrium salicylate, yttrium 3,5-di-t-butylsalicylate; yttrium amides such as yttrium dimethylamide, yttriumdiethylamide, yttrium diphenylamide, yttrium bis(trimethylsilyl)amideand the like; yttrium acetylacetonate and yttriumt-butylacetylacetonate.

d) hafnium alkyls such as such as tetraethyl hafnium, tetrabutylhafnium, tetrabenzyl hafnium and the like; hafnium alkoxides such ashafnium tetramethoxide, hafnium tetraethoxide, hafniumtetraisopropoxide, hafnium tetra-t-butoxide, hafnium tetra-sec-butoxideand the like; hafnium aryloxides such as hafnium phenoxide and hafniumphenoxides in which one or more of the phenoxide groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like; hafnium carboxylates such as hafnium formate,hafnium acetate, hafnium propionate, hafnium 2-ethylhexanoate, hafniumbenzoate, hafnium benzoates in which one or more of the benzoate groupsis ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like, hafnium salicylate, hafnium 3,5-di-t-butylsalicylate; hafnium amides such as hafnium tetra(dimethylamide), hafniumtetra(diethylamide), hafnium tetra(diphenylamide), hafniumtetra((bistrimethylsilyl)amide); hafnium acetylacetonate and hafniumt-butylacetylacetonate.

e) titanium alkyls such as such as tetraethyl titanium, tetrabenzyltitanium and the like; titanium alkoxides such as titaniumtetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide,titanium tetra-t-butoxide, titanium tetra-sec-butoxide and the like;titanium aryloxides such as titanium phenoxide and titanium phenoxidesin which one or more of the phenoxide groups is ring-substituted withalkyl, CF₃, cyano, COCH₃, halogen, hydroxyl, alkoxyl and the like;titanium carboxylates such as titanium formate, titanium acetate,titanium propionate, titanium 2-ethylhexanoate, titanium benzoate,titanium benzoates in which one or more of the benzoate groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like, titanium salicylate, titanium 3,5-di-t-butylsalicylate; titanium amides such as titanium tetra(dimethylamide),titanium tetra(diethylamide, titanium tetra(diphenylamide), titaniumtetra((bistrimethylsilyl)amide); titanium acetylacetonate and titaniumt-butylacetylacetonate.

f) zirconium alkyls such as such as tetraethyl zirconium, tetrabutylzirconium, tetrabenzyl zirconium and the like; zirconium alkoxides suchas zirconium tetramethoxide, zirconium tetraethoxide, zirconiumtetraisopropoxide, zirconium tetra-t-butoxide, zirconiumtetra-sec-butoxide and the like; zirconium aryloxides such as zirconiumphenoxide and zirconium phenoxides in which one or more of the phenoxidegroups is ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen,hydroxyl, alkoxyl and the like; zirconium carboxylates such as zirconiumformate, zirconium acetate, zirconium propionate, zirconium2-ethylhexanoate, zirconium benzoate, zirconium benzoates in which oneor more of the benzoate groups is ring-substituted with alkyl, CF₃,cyano, COCH₃, halogen, hydroxyl, alkoxyl and the like, zirconiumsalicylate, zirconium 3,5-di-t-butyl salicylate; zirconium amides suchas zirconium tetra(dimethylamide), zirconium tetra(diethylamide,zirconium tetra(diphenylamide), zirconiumtetra((bistrimethylsilyl)amide); zirconium acetylacetonate and zirconiumt-butylacetylacetonate.

g) vanadium alkoxides such as vanadium methoxide, vanadium ethoxide,vanadium isopropoxide, vanadium t-butoxide, vanadium sec-butoxide andthe like; vanadium oxo tris(alkoxides) such as vanadium oxotris(methoxide), vanadium oxo tris(ethoxide), vanadium oxotris(isopropoxide), vanadium oxo tris(t-butoxide), vanadium oxotris(sec-butoxide) and the like; vanadium aryloxides such as vanadiumphenoxide and vanadium phenoxides in which one or more of the phenoxidegroups is ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen,hydroxyl, alkoxyl and the like; vanadium carboxylates such as vanadiumformate, vanadium acetate, vanadium propionate, vanadium2-ethylhexanoate, vanadium benzoate, vanadium benzoates in which one ormore of the benzoate groups is ring-substituted with alkyl, CF₃, cyano,COCH₃, halogen, hydroxyl, alkoxyl and the like, vanadium salicylate,vanadium 3,5-di-t-butyl salicylate; vanadium tris(acetylacetonate) andvanadium tris(t-butylacetylacetonate); vanadium oxobis(acetylacetonate).

h) zinc alkyls such as such as dimethyl zinc, diethyl zinc, dibutylzinc, dibenzyl zinc and the like; alkyl zinc alkoxides such as ethylzinc isopropoxide; zinc alkoxides such as zinc methoxide, zinc ethoxide,zinc isopropoxide, zinc t-butoxide, zinc sec-butoxide and the like; zincaryloxides such as zinc phenoxide and zinc phenoxides in which one ormore of the phenoxide groups is ring-substituted with alkyl, CF₃, cyano,COCH₃, halogen, hydroxyl, alkoxyl and the like; zinc carboxylates suchas zinc formate, zinc acetate, zinc propionate, zinc 2-ethylhexanoate,zinc benzoate, zinc benzoates in which one or more of the benzoategroups is ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen,hydroxyl, alkoxyl and the like, zinc salicylate, zinc 3,5-di-t-butylsalicylate; zinc amides such as zinc dimethylamide, zinc diethylamide,zinc diphenylamide, zinc (bistrimethylsilyl)amide; zinc acetylacetonateand zinc t-butylacetylacetonate.

i) trialkyl aluminum compounds such as trimethylaluminum, triethylaluminum, tributyl aluminum, tribenzylaluminum and the like; aluminumalkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminumtriisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide,aluminum tri-sec-butoxide and the like; aluminum aryloxides such asaluminum phenoxide and aluminum phenoxides in which one or more of thephenoxide groups is ring-substituted with alkyl, CF₃, cyano, COCH₃,halogen, hydroxyl, alkoxyl and the like; aluminum carboxylates such asaluminum formate, aluminum acetate, aluminum propionate, aluminum2-ethylhexanoate, aluminum benzoate, aluminum benzoates in which one ormore of the benzoate groups is ring-substituted with alkyl, CF₃, cyano,COCH₃, halogen, hydroxyl, alkoxyl and the like, aluminum salicylate,aluminum 3,5-di-t-butyl salicylate; aluminum amides such as aluminumtris(dimethylamide), aluminum tris(diethylamide), aluminumtris(diphenylamide), aluminum tris(di(trimethylsilyl)amide) and thelike; aluminum acetylacetonate; aluminum t-butylacetylacetonate; andalkylaluminum oxides and alkoxides such as diethylaluminum ethoxide,dimethylaluminum ethoxide, diethylaluminum isopropoxide,dimethylaluminum isopropoxide, methyl aluminoxane,tetraethyldialuminoxane and the like. In exemplary embodiments, use ofaluminum carboxylates such as aluminum formate, aluminum acetate,aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate,aluminum benzoates in which one or more of the benzoate groups isring-substituted with alkyl may be avoided.

j) trialkyl gallium compounds such as trimethylgallium, triethylgallium, tributyl gallium, tribenzylgallium and the like; galliumalkoxides such as gallium trimethoxide, gallium triethoxide, galliumtriisopropoxide, gallium tri-t-butoxide, gallium tri-sec-butoxide andthe like; gallium aryloxides such as gallium phenoxide and galliumphenoxides in which one or more of the phenoxide groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like; gallium carboxylates such as gallium formate,gallium acetate, gallium propionate, gallium 2-ethylhexanoate, galliumbenzoate, gallium benzoates in which one or more of the benzoate groupsis ring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like, gallium salicylate, gallium 3,5-di-t-butylsalicylate; gallium amides such as gallium tris(dimethylamide), galliumtris(diethylamide), gallium tris(diphenylamide), galliumtris(di(trimethylsilyl)amide) and the like; gallium acetylacetonate;gallium t-butylacetylacetonate; and alkylgallium alkoxides such asdiethylgallium ethoxide, dimethylgallium ethoxide, diethylgalliumisopropoxide and dimethylgallium isopropoxide;

k) trialkyl indium compounds like trimethyl indium; indium alkoxidessuch as indium methoxide, indium ethoxide, indium isopropoxide, indiumt-butoxide, indium sec-butoxide and the like; indium aryloxides such asindium phenoxide and indium phenoxides in which one or more of thephenoxide groups is ring-substituted with alkyl, CF₃, cyano, COCH₃,halogen, hydroxyl, alkoxyl and the like; indium carboxylates such asindium formate, indium acetate, indium propionate, indium2-ethylhexanoate, indium benzoate, indium benzoates in which one or moreof the benzoate groups is ring-substituted with alkyl, CF₃, cyano,COCH₃, halogen, hydroxyl, alkoxyl and the like, indium salicylate,indium 3,5-di-t-butyl salicylate; indium acetylacetonate; and indiumt-butylacetylacetonate; and

1) stannous phosphate; stannous pyrophosphate, stannous alkoxides suchas stannous methoxide, stannous ethoxide, stannous isopropoxide,stannous t-butoxide, stannous sec-butoxide and the like; stannousaryloxides such as stannous phenoxide and stannous phenoxides in whichone or more of the phenoxide groups is ring-substituted with alkyl, CF₃,cyano, COCH₃, halogen, hydroxyl, alkoxyl and the like; stannouscarboxylates such as stannous formate, stannous acetate, stannouspropionate, stannous 2-ethylhexanoate, stannous benzoate, stannousbenzoates in which one or more of the benzoate groups isring-substituted with alkyl, CF₃, cyano, COCH₃, halogen, hydroxyl,alkoxyl and the like, stannous salicylate, stannous 3,5-di-t-butylsalicylate; stannous acetylacetonate; and stannoust-butylacetylacetonate.

In addition to the foregoing, other suitable MG3-15LA compounds includemagnesium, Group 3-Group 15, or lanthanide series metal alkoxides,whereas one or more of the alkoxide group(s) are the conjugate base,after removal of one or more hydroxyl hydrogen atoms, from (1) aninitiator compound as described below, (2) a polyether monol orpolyether polyol product of the polymerization reaction or (3) apolyether having a molecular weight intermediate to the initiator andthe polyether monol or polyether polyol product of the polymerization.

Polyurethane Products

The polycarbonate based polyol, such as the poly(ether-carbonate)polyol, is useful to make a wide variety of polyurethane products, suchas slabstock foams, molded foams, flexible foams, viscoeleastic foams,combustion modified foams, rigid foams, elastomers, adhesives, sealants,and/or coatings. The polyurethane product may be useful in a variety ofpackaging applications, comfort applications (such asmattresses—including mattress toppers, pillows, furniture, seatcushions, etc.), shock absorber applications (such as bumper pads, sportand medical equipment, helmet liners, etc.), thermal insulationapplications, electro-conductivity for anti-static packaging ofelectronic goods, and noise and/or vibration dampening applications(such as earplugs, automobile panels, etc.)

The polyurethane product may be prepared as the reaction product of apolyurethane forming formulation that includes an isocyanate componentand an isocyanate-reactive component. The isocyanate component mayinclude one or more polyisocyanates, one or more isocyanate-terminatedprepolymers, and/or a combination thereof. The poly(ether-carbonate)polyol may be the only polyol or one of two or more polyols (e.g., toadjust the solids content to a desired level or provide particularcharacteristics to the polyurethane) included in the isocyanate-reactivecomponent. The isocyanate-reactive component and/or theisocyanate-component may further include at least one additive.Exemplary additives include catalysts, surfactants, blowing agents, andother additives for polyurethanes as would be known to a person ofordinary skill in the art.

With respect to the isocyanate component, exemplary isocyanates includearomatic, cycloaliphatic, and aliphatic isocyanates, andisocyanate-terminated prepolymer derived from at least one selected fromthe group of aromatic, cycloaliphatic, and aliphatic isocyanates. Theamount of isocyanate component used in making a polyurethane product iscommonly expressed in terms of isocyanate index. The isocyanate index isdefined as the molar stoichiometric excess of isocyanate moieties in areaction mixture with respect to the number of moles ofisocyanate-reactive units (active hydrogens available for reaction withthe isocyanate moiety), multiplied by 100. An isocyanate index of 100means that there is no stoichiometric excess, such that there is 1.0mole of isocyanate groups per 1.0 mole of isocyanate-reactive groups,multiplied by 100. In embodiments, the isocyanate index may range fromabout 70 to 400.

With respect to the isocyanate-reactive component, the polycarbonatebased polyol may be blended with one or more additional polyols. Forexample, the polycarbonate based polyol may comprise from 5 wt % to 90wt % (e.g., 5 wt % to 80 wt %, 10 wt % to 70 wt %, 10 wt % to 60 wt %,15 wt % to 50 wt %, 15 wt % to 40 wt %, 15 wt % to 30 wt %, 15 wt % to25 wt %, etc.) of the isocyanate-reactive component. The additionalpolyol, may be a polyether polyol having a nominal hydroxylfunctionality of 2 to 8 and a number average molecular weight from 1,000g/mol to 20,000 g/mol.

Various additives may be added to the reaction mixture for forming thepolyurethane product to adjust characteristics of the resultant product,e.g., additives known to those of ordinary skill in the art may be used.Additives may be added as part of the isocyanate component and/or theisocyanate-reactive component. Exemplary additives include a catalyst,an adhesion promoter, a surfactant, a moisture scavenger, a cell opener,an antioxidant, a curative, a pH neutralizer, a UV stabilizer, anantistatic agent, a plasticizer, a compatibilizer, a filler, areinforcing agent, a flame retardant, pigments/dyes, a mold releaseagent, and/or a crosslinker.

If the polyurethane product is a foam, product may be formed using aone-shot method, such a slabstock process (e.g., as free rise foam), amolding process (such as in a box foaming process), or any other processknown in the art. In a slabstock process, the components may be mixedand poured into a trough or other region where the formulation reacts,expands freely in at least one direction, and cures. Slabstock processesmay be operated continuously at commercial scales. In a molding process,the components may be mixed and poured into a mold/box (heated ornon-heated) where the formulation reacts, expands without the mold in atleast one direction, and cures.

The polyurethane foam may be prepared at initial ambient conditions(i.e., room temperature ranging from 20° C. to 25° C. and standardatmospheric pressure of approximately 1 atm). For example, thepolyurethane foam may include the solid functional additive (e.g., apolymer that has a melting point above 100° C.), added via the modifiedcopolymer polyol, without requiring heating or application of pressureto the isocyanate-reactive component. Foaming at pressure belowatmospheric condition can also be done, to reduce foam density andsoften the foam. Foaming at pressure above atmospheric condition can bedone, to increase foam density and therefore the foam load bearing asmeasured by indentation force deflection (IFD). In a molding processing,the polyurethane foam may be prepared at initial mold temperature aboveambient condition, e.g., 50° C. and above. Overpacking of mold, i.e.filling the mold with extra foaming material, can be done to increasefoam density.

The following examples are provided to illustrate the invention, but arenot intended to limit the scope thereof. All parts and percentages areby weight unless otherwise indicated. All molecular weight values arebased on number average molecular weight, unless indicated otherwise.

EXAMPLES

Approximate properties, characters, parameters, etc., are provided belowwith respect to various working examples, comparative examples, and thematerials used in the working and comparative examples.

Preparation of Polycarbonate Based Polyols

The following materials are principally used:

-   DMC A zinc hexacyanocobaltate catalyst complex (exemplary grades    available from Bayer Material Science).-   Starter 1 A propoxylated polyol that is glycerin-initiated, having a    number average molecular weight of 700 g/mol and a nominal hydroxyl    functionality of 3 (available from The Dow Chemical Company).-   Starter 2 A propoxylated polyol that is glycerin-initiated, having a    number average molecular weight of 450 g/mol and a nominal hydroxyl    functionality of 3 (available from The Dow Chemical Company).-   Starter 3 A propoxylated polyols that is propylene glycol-initiated,    having a number average molecular weight of 400 g/mol and a nominal    hydroxyl functionality of 2 (available from The Dow Chemical    Company).-   Promoter 1 Aluminum triisopropoxide (Al(O-iPr)₃), available from    Acros Organics.-   Promoter 2 Aluminum-tri-sec-butoxide (Al(OBu)₃), available from    Gelest, Inc.-   Promoter 3 Hafnium(IV) tert-butoxide (Hf(OBu)₄), available from    Gelest, Inc.-   Promoter 4 Magnesium di-tert-butoxide (Mg(OBu)₂), available from    Sigma Aldrich.-   Promoter 5 Gallium(III) ethoxide (Ga(OEt)₃), available from Gelest,    Inc.-   Promoter 6 Indium(III) ethoxide (In(OEt)₃), available from Alfa    Aesar.-   Promoter 7 Titanium(IV) ethoxide (Ti(OEt)₄), available from Gelest,    Inc.

Various Examples are discussed below:

Examples 1 to 3—Promoter Vs. No Promoter

For each of Examples 1 to 3, during a preliminary stage, the reactor isheated to 130° C. and purged continuously with nitrogen for 1.5 hours todry the contents of the reactor, which occurs after the addition of theDMC, Starter 1, and the Promoter 1 (if used), but before addition of anypropylene oxide. Then, the reactor is heated to 150° C. and an initialcharge of 18.4 mL of propylene oxide is added for catalyst activation.The pressure in the reactor increases to an initial pressure of 11.7psig and upon catalyst activation the pressure declines to less than 2psig. The reactor is then cooled to 100° C. and taken to 70 psig byfeeding carbon dioxide and then venting. This process of feeding andventing carbon dioxide is further repeated twice. During thepolymerization stage, the pressure is increased to 105 psig byco-feeding the propylene oxide and carbon dioxide into the reactor atthe molar ratio provided in Table 1. Then, the co-feeding is stopped andfor the first digestion stage the pressure in the reactor is allowed todecrease to 95 psig. Prior to the second digestion stage, the additionof propylene oxide and carbon dioxide is started again at the same molarratio and continued until the reactor pressure increases again to 105psig. Then, again, the co-feeding is stopped and for the seconddigestion stage the pressure in the reactor is allowed to decrease to 95psig. For each reactant addition cycle, the time required for thereactor pressure to decline from 105 psig to 95 psig, which isindicative of the catalytic activity, is shown in Table 1 below. Afterthe reactor pressure had declined to 95 psig for the second time, nomore reactants are added. The pressure profile in the reactor isfollowed, and once stabilized (i.e., no further change), the reactor iscooled and the reactor pressure is vented. The contents of the reactorare purged with nitrogen for 30 minutes with stirring to removeunreacted propylene oxide, carbon dioxide, and volatile organiccompounds. The product is analyzed via GPC and NMR.

Example 1

A sample of 0.05 grams of DMC is dissolved in 99.6 grams of the Starter1 and then dried in a 1 liter capacity reactor according to the generalprocedure outlined above. Then, the reactor is heated to 150° C. and aninitial charge of 18.4 mL of propylene oxide is added for catalystactivation. The pressure in the reactor initially increases to 11.7 psigand upon catalyst activation the pressure declines to less than 2 psig.The reactor is then cooled to 100° C. and taken to 70 psig by feedingcarbon dioxide and then venting. This process of feeding and ventingcarbon dioxide is further repeated twice. Next, during the subsequentpolymerization stage, a total of 2.7 g of propylene oxide and 2 grams ofcarbon dioxide are added over a period of 3 hours under polymerizationconditions.

Example 2

A sample of 0.05 grams of DMC is dissolved in 99.6 grams of the Starter1 and then dried in a 1 liter capacity reactor according to the generalprocedure outlined above. Then, the reactor is heated to 150° C. and aninitial charge of 18.4 mL of propylene oxide is added for catalystactivation. The pressure in the reactor initially increases to 11.7 psigand upon catalyst activation the pressure declines to less than 2 psig.The reactor is then cooled to 100° C. and taken to 70 psig by feedingcarbon dioxide and then venting. This process of feeding and ventingcarbon dioxide is further repeated twice. Next, during the subsequentpolymerization stage, a total of 61.5 grams of propylene oxide and 10.1grams of carbon dioxide are added over a period of 2.5 hours underpolymerization conditions.

Example 3

A sample of 0.05 grams of DMC and 0.5 grams of Promoter 1 are dissolvedin 99.6 grams of the Starter 1 and then dried in a 1 liter capacityreactor according to the general procedure outlined above. Then, thereactor is heated to 150° C. and an initial charge of 18.4 mL ofpropylene oxide is added for catalyst activation. The pressure in thereactor initially increases to 11.7 psig and upon catalyst activationthe pressure declines to less than 2 psig. The reactor is then cooled to100° C. and taken to 70 psig by feeding carbon dioxide and then venting.This process of feeding and venting carbon dioxide is further repeatedtwice. Next, during the subsequent polymerization stage, a total of 75.9grams of propylene oxide and 12.5 grams of carbon dioxide are added overa period of 2.5 hours under polymerization conditions.

TABLE 1 NMR GPC Activity CO₂:PO CO₂ in wt % MW of 1^(st) 2^(nd) feedpoyol by- polyol digestion digestion Ex. ratio Catalyst Activity mol %product (g/mol) (min) (min) 1 1:1 DMC No — — — — — 2 1:5 DMC Yes 0.1 01084 52 60 3 1:5   DMC + Yes 3.4 0.4 1227 8 10 Promoter 1

Referring to the above, the use of the promoter appears to be able toimprove the process when using the DMC catalyst, as compared to the casewhen the promoter is not present. For example, with respect to Example3, the activity increased by an approximate factor of 6 and the carbondioxide incorporation increased by an approximate factor of 34 whencompared Example 2. In particular, Example 3 resulted in a polyol yieldof 99.6%.

Examples 4 to 6—Varying Amounts of Promoter

During a preliminary stage, predefined amounts of DMC catalyst and thePromoter 1, in amounts as shown in Table 2, are dissolved in 144 gramsof the Starter 1 and then dried in a 1 L capacity reactor by heating to130° C. and purging continuously with nitrogen for 2 hours. Then, thereactor is heated to 150° C. and an initial charge of 21.6 grams ofpropylene oxide are added for catalyst activation. The pressure in thereactor is initially increased to approximately 10 psig and uponcatalyst activation the pressure declines to less than 2 psig. Thereactor is then cooled to reaction temperature (T) provided in Table 2and the pressure is taken to 70 psig by feeding carbon dioxide and thenventing. This process of feeding and venting carbon dioxide is furtherrepeated twice.

Then, the pressure is increased or decreased to reaction pressure (P)provided in Table 2, which initiates the polymerization stage. Duringthe polymerization stage, propylene oxide is fed at a rate of 1 mL/minuntil the amount listed in Table 2 (Oxide) is reached. During the oxidefeed, the pressure in the reactor shown in Table 2 is maintained byfeeding CO₂ on demand when the pressure drops 2.5 psi below the targetpressure and the CO₂ feed is stopped when the reactor reached a pressure2.5 psi higher than the target pressure. After the propylene oxide feedis stopped, the pressure is maintained by feeding carbon dioxide anddigesting until the pressure in the reactor does not change anymore.Then, the reactor is cooled to room temperature and the reactor pressureis vented. The contents of the reactor are purged with nitrogen for 30minutes to remove unreacted propylene oxide and carbon dioxide. Theproduct is analyzed by GPC and NMR.

TABLE 2 CO₂ Polyol DMC Promoter 1 T P Oxide content selectivity Mn Exgrams grams ° C. psig grams wt % wt % g/mol PDI 4 0.015 0.056 150  60282.61 0.3 99.0 1910 1.06 5 0.05 0.466  90 120 283.00 10.4 95.9 20261.14 6 0.05 0.186  90  60 282.43 7.4 96.7 2013 1.07

Referring to Table 2, Examples 4 to 6 demonstrate that the combinationof DMC catalyst and promoter enables the incorporation of carbon dioxideinto polyether polyols at levels from 0.3 wt % to 10.4 wt % according tothe provided definition under mild temperature and pressure conditionsby first activating the catalyst combination under nitrogen andthereafter adding carbon dioxide at low pressures. The promoter and theDMC catalyst may be present at a weight ratio of 1:1 to 20:1 (e.g., 2:1to 15:1, 3:1 to 12:1, 4:1 to 10:1, etc.).

Examples 7 to 12—Varying Temperatures and Pressures

During a preliminary stage, DMC catalyst (0.027 grams) and the Promoter2, in amounts as shown in Table 3, are mixed with 140 grams of theStarter 1 in a bottle under dry conditions and sonicated for 45 minutes.The contents of the bottle are added to a 1 L capacity reactor andstirred for the entire time of the process that ensued. Then, thereactor is heated to 130° C. and purged continuously with nitrogen for 2hours. After closing the reactor vent and stopping the nitrogen flow,the temperature in the reactor is increased to 140° C. while thepressure is taken to 70 psig by feeding carbon dioxide and then venting.This process of feeding and venting carbon dioxide is further repeatedtwice.

Then, the reactor is taken to 60 psig by feeding carbon dioxide and aninitial charge of 15.6 grams of propylene oxide is added to the reactorfor catalyst activation. The pressure in the reactor initially increasesby approximately 10-20 psig, and upon catalyst activation the pressuredeclines back to approximately 60-65 psig. The reactor is then taken tothe temperature (T) and pressure (P) defined in Table 3, which initiatesthe polymerization stage. During the polymerization stage, propyleneoxide is fed at a rate of 1 mL/min and stopped when 259 grams ofpropylene oxide have been fed. During the oxide feed, the pressure inthe reactor shown in Table 3 is maintained by feeding carbon dioxide ondemand when the pressure drops 2.5 psi below the target pressure and thecarbon dioxide feed is stopped when the reactor reached a pressure 2.5psi higher than the target pressure. After the propylene oxide feed isstopped, the pressure is maintained by feeding carbon dioxide anddigesting until the pressure in the reactor does not change anymore.Then, the reactor is cooled to room temperature and the reactor pressureis vented. The contents of the reactor are purged with nitrogen for 30minutes under stirring to remove unreacted propylene oxide and carbondioxide. The product is analyzed via GPC and NMR.

TABLE 3 Total Promoter CO₂ Polyol Activation Digestion Batch 2 T Pcontent selectivity Mn Time Time Time Ex. grams ° C. psig wt % wt %g/mol PDI [hh:mm] [hh:mm] [hh:mm] 7 0 110 100 5.9 96.5 1956 1.47 1:05 6:50 15:44 8 0.153 110 100 6.8 97.3 2120 1.04 1:19  0:30  5:42 9 0.07680 140 4.9 97.6 1191 1.14 5:48  0:17  6:05 10 0.229 80 140 15.1 97.62131 1.22 5:29 14:44 22:33 11 0.076 80  60 9.8 98.9 2066 1.12 1:53  7:2512:11 12 0.076 140  60 0.8 98.2 2067 1.02 1:07  0:10  5:24

Referring to Table 3, Example 7 is a comparative example of the sameprocess operated in Example 8, but without the addition of a promoter.Example 7 requires a significantly longer digest time and overall batchtime compared to the identical process run with the addition of apromoter.

In particular, Examples 7 to 12 demonstrate that the process accordingto exemplary embodiments may be successfully initiated and operated byfirst activating the DMC catalyst by adding an oxides such propyleneoxide under carbon dioxide in the presence of a promoter, and thencontinuing to add the oxide and carbon dioxide under mild temperatureand pressure conditions. This process enables the elimination of aseparate catalyst activation step performed under a nitrogen atmosphere.Further, the process allows the immediate activation of DMC catalystunder mild carbon dioxide pressure followed by continuous addition ofoxides and carbon dioxide until the process (e.g., semi-batch process)is complete. Thus, saving valuable reactor time.

Examples 13 to 17—Varying Promoters

During a preliminary stage, DMC catalyst (0.028 grams) and a promoter(the type and amount according to Table 4) are mixed with 144 grams ofthe Starter 1 in a bottle under dry conditions and sonicated for 45minutes. The contents of the bottle are added to a 1 L capacity reactorand stirred for the entire time of the process that ensued. Then, thereactor is heated to 130° C. and purged continuously with nitrogen for 2hours. After closing the reactor vent and stopping the nitrogen flow,the temperature in the reactor is increased to 140° C. while thepressure is taken to 70 psig by feeding carbon dioxide and then venting.This process of feeding and venting carbon dioxide is further repeatedtwice.

Then, the reactor is taken to 60 psig by feeding carbon dioxide and aninitial charge of 16.0 grams of propylene oxide is added to the reactorfor catalyst activation. The pressure in the reactor initially increasedby approximately 10-20 psig, and upon catalyst activation the pressuredeclined back to approximately 60-65 psig. The reactor is then taken to110° C. and 100 psig by feeding carbon dioxide. During thepolymerization stage, propylene oxide is fed at a rate of 1 mL/min andstopped when 266.8 grams of propylene oxide have been fed. During theoxide feed, the pressure in the reactor defined above is maintained byfeeding carbon dioxide on demand when the pressure drops 2.5 psi belowthe target pressure and the carbon dioxide feed is stopped when thereactor reached a pressure 2.5 psi higher than the target pressure.After the propylene oxide feed is stopped, the pressure is maintained byfeeding carbon dioxide and digesting until the pressure in the reactordid not change anymore. Then, the reactor is cooled to room temperatureand the reactor pressure is vented. The content of the reactor is purgedwith nitrogen for 30 minutes under stirring to remove unreactedpropylene oxide and carbon dioxide. The product is analyzed by GPC andNMR.

TABLE 4 Total CO₂ Polyol Activation Digestion Batch Promoter contentselectivity Mn PDI Time Time Time Ex. grams wt % wt % g/mol [−] [hh:mm][hh:mm] [hh:mm] 13 Promoter 3 0.292 6.1 96.5 1942 1.25 3:00 7:03 12:5014 Promoter 4 0.110 6.5 96.6 1969 1.32 3:52 4:18 10:54 15 Promoter 50.130 7.6 97.0 1972 1.58 2:42 3:53  9:41 16 Promoter 6 0.160 5.5 96.01944 1.19 3:17 5:30 10:59 17 Promoter 7 0.217 4.9 96.2 1857 1.28 4:277:40 14:03

Referring to Table 4, it is shown that the process according toexemplary embodiments with the use of different types of promoters.

Example 18—Varying Oxides

During a preliminary stage, DMC catalyst (0.454 grams) and the Promoter2 (2.538 grams) are mixed with 908 grams of the Starter 2 in a bottleunder dry conditions and sonicated for 45 minutes. The content of thebottle are added to a 6 L capacity reactor and stirred for the entiretime of the process that ensued. Then, the reactor is heated to 130° C.and purged continuously with nitrogen for 2 hours. After closing thereactor vent and stopping the nitrogen flow, the temperature in thereactor is increased to 140° C. while the pressure is taken to 70 psigby feeding carbon dioxide and then venting. This process of feeding andventing carbon dioxide is further repeated twice.

Then, the reactor is taken to 60 psig by feeding carbon dioxide and aninitial charge of 100.8 grams of propylene oxide is added to the reactorfor catalyst activation. The pressure in the reactor initially increasesby about 10-20 psig, and upon catalyst activation the pressure declinesback to 60-65 psig. The reactor is then taken to 105° C. and 90 psig byfeeding carbon dioxide. During the polymerization stage, propylene oxideis fed at 12 mL/min and ethylene oxide is fed at 1.62 g/min until atotal of 4162 grams of propylene oxide and 672 grams of ethylene oxideare fed. During the oxide feed, the pressure in the reactor shown inTable 3 is maintained by feeding carbon dioxide on demand when thepressure drops 2.5 psi below the target pressure and the carbon dioxidefeed is stopped when the reactor reached a pressure 2.5 psi higher thanthe target pressure. After the propylene oxide and ethylene oxide feedsare stopped, the pressure is maintained by feeding carbon dioxide anddigesting until the pressure is maintained by feeding carbon dioxide anddigesting until the pressure in the reactor does not change anymore.Then, the reactor is cooled to room temperature and the reactor pressureis vented. The contents of the reactor are purged with nitrogen for 30minutes under stirring to remove unreacted propylene oxide, ethyleneoxide, and carbon dioxide. The resulting polyol product has a numberaverage molecular weight of 2837 g/mole by GPC analysis, and contains5.2 weight percent CO₂ with a polyol selectivity of 96.7%.

Example 18 demonstrates that polyols containing ethylene oxide,propylene oxide, and carbon dioxide may be prepared to a targeted weight% composition of carbon dioxide, and the resulting polyol makes goodquality flexible polyurethane foam when compared to a similar polyetherpolyol that is not made with any carbon dioxide.

The polyol of Example 18 is further tested for use in exemplarypolyurethane formulations. In particular, Example 18 is combined withTDI (which is commercially available as VORANATE™ from The Dow ChemicalCompany) in the formulation of Table 5 to prepare a flexiblepolyurethane foam. The foam of the formulation is compared to a similarpolyether polyol of similar hydroxyl equivalent weight and weightpercent of ethylene oxide content, but without the inclusion of carbondioxide as a co-reactant. The polyol of the comparative example isprepared with VORANOL™ 8136, a commercial polyol prepared with a DMCcatalyst available from The Dow Chemical Company.

To prepare the foam examples for Examples 19 to 21 in Table 5, woodenboxes of 38 cm×38 cm×24 cm are used for box foaming, which were linedwith plastic film for easy demolding. A high shear pin shape mixer isused to mix the materials. The components except KOSMOS® 29 andVORANATE™ T-80 TDI are mixed at a speed of 2400 rpm for 15 seconds.Then, the KOSMOS® 29 is added with additional mixing of 15 seconds at2400 rpm. Next, the TDI is added with additional mixing for 3 seconds ata high speed of 3,000 rpm. The resultant mixture is then poured into thebox. The foam is allowed to cure overnight before cutting and testing.Referring to Table 5, Examples 19 and 20 are prepared using commerciallyavailable polyols. Example 21 is prepared using the Polyol for Example18, according to exemplary embodiments.

TABLE 5 Examples 19 20 21 Components (parts by weight) VORANOL ™ 3136100 VORANOL ™ 8136 100 Polyol Example 18 100 Water 4.5 4.5 4.5 Niax ®L-618 0.6 0.6 0.6 DABCO ® BLV 0.15 0.15 0.15 KOSMOS ® 29 0.2 0.2 0.2VORANATE ™ T-80 TDI 55.0 55.0 55.0

Foam properties for Examples 19 to 20 are shown below in Table 6.

TABLE 6 Example 19 20 21 Airflow-dm3/s-ASTM D 3574 G Mean (cu_ft/min)6.07 4.73 3.48 CFD ISO-3386-ISO 3386/1 Mean 25% (kPa) 8.81 10.26 11.15Mean 40% (kPa) 9.57 11.27 12.34 Mean 65% (kPa) 15.63 18.36 20.28 CS 90%,Original, Parallel-ASTM D 3574-03/D CT (%) 2.90 3.35 4.34 CD (%) 3.203.70 4.79 Free Rise Density-ASTM D1622-03 Density (lbm/cu ft) 1.4921.509 1.564 IFD: ASTM D 3574-01-Test B Load @ 25% Deflection (lbf) 42.2347.02 50.57 Load @ 65% Deflection (lbf) 79.47 90.47 99.41 Load @ 25%Return (lbf) 27.37 29.83 33.33 Support Factor (%) 1.88 1.92 1.97Hysteresis (%) 64.81 63.45 65.92 Resilience (Ball Rebound) Test-ASTMD-3574-H Average Resiliency (%) 38 35 34 Tear-ASTM D 3574-01 Test F Tearstrength mean (lbf/in) 2.36 1.97 1.81 Tensile: (D3574)-ASTM D 3574-01Test E Tensile strength mean (psi) 16.34 18.85 19.77 Elongation at break(mean), % (%) 173.59 163.95 148.52

As shown in Table 6, a flexible polyurethane foam prepared from thepolyol of Example 18 has physical properties that are very similar tothe properties of a flexible polyurethane foam prepared from a polyolcontaining no CO₂.

Example 22-23—Polyols with Varying Molecular Weight and Functionality

During a preliminary stage, DMC catalyst (0.0461 grams) and Promoter 2(0.258 grams) are mixed with 135 grams of the Starter 3 in a bottleunder dry conditions and sonicated for 45 minutes. The contents of thebottle are added to a 1 L capacity reactor and stirred for the entiretime of the process that ensued. Then, the reactor is heated to 130° C.and purged continuously with nitrogen for 2 hours. After closing thereactor vent and stopping the nitrogen flow, the temperature in thereactor is increased to 140° C. while the pressure is taken to 70 psigby feeding carbon dioxide and then venting. This process of feeding andventing carbon dioxide is further repeated twice.

Then, the reactor is taken to 60 psig by feeding carbon dioxide and aninitial charge of 15 grams of propylene oxide is added to the reactorfor catalyst activation. The pressure in the reactor initially increasedby approximately 10-20 psig, and upon catalyst activation the pressuredeclined back to approximately 60-65 psig. The reactor is then taken to110° C. and 100 psig by feeding carbon dioxide. During thepolymerization stage, propylene oxide is fed at a rate of 1.5 mL/min andstopped when a total of 538.7 grams of propylene oxide have been fed.During the oxide feed, the pressure in the reactor defined above ismaintained by feeding carbon dioxide on demand when the pressure drops2.5 psi below the target pressure and the carbon dioxide feed is stoppedwhen the reactor reached a pressure 2.5 psi higher than the targetpressure. After the propylene oxide feed is stopped, the pressure ismaintained by feeding carbon dioxide and digesting until the pressure inthe reactor did not change anymore. Then, the reactor is cooled to roomtemperature and the reactor pressure is vented. The content of thereactor is purged with nitrogen for 30 minutes under stirring to removeunreacted propylene oxide and carbon dioxide. The product is analyzed byGPC and NMR. Results are shown in Table 7, below.

TABLE 7 CO₂ content Polyol selectivity Mn Ex. wt % wt % g/mol PDI 225.88 97.02 2837 1.15 23 5.06 92.56 2191 1.05

Examples 22 and 23 further illustrate that polyols of differentmolecular weight, functionality and carbon dioxide content can beprepared according exemplary embodiments.

Examples 24 and 25—Preparing Polyols at High Pressures

According to exemplary embodiments, the poly(ether-carbonate) polyolscan be prepared at low pressures, which is desirable for industrialscale operations. Though, the embodiments also include preparing suchpolyols at high pressures.

During a preliminary stage, the amounts of DMC catalyst, Promoter 2, andStarter 1 are mixed in the amounts shown in Table 7 in a bottle underdry conditions and sonicated for 1 hour. The contents of the bottle areadded to a 1.8 L capacity reactor and stirred for the entire time of theprocess that ensued. Then, the reactor is heated to 130° C. and purgedcontinuously with nitrogen for 3 hours. After closing the reactor ventand stopping the nitrogen flow, the temperature in the reactor isincreased to 140° C. while the pressure is taken to 70 psig by feedingcarbon dioxide and then venting. This process of feeding and ventingcarbon dioxide is further repeated twice.

Then, the reactor is taken to 70 psig by feeding carbon dioxide and aninitial charge of propylene oxide in the amount shown in Table 8 isadded to the reactor for catalyst activation. The pressure in thereactor initially increased by about 10-20 psig (0.0689-0.138 MPa), andupon catalyst activation the pressure declined back to 70-75 psig. Thereactor is then taken to 110° C. and to the pressure defined in Table 8by feeding carbon dioxide. Once the target reactor pressure is reached,propylene oxide is fed at the flow rates shown in Table 8 and stoppedwhen a total amount of propylene oxide shown in Table 8 has been fed.During the oxide feed, the pressure in the reactor defined above ismaintained by feeding carbon dioxide on demand when the pressure drops2.5 psi below the target pressure and the carbon dioxide feed is stoppedwhen the reactor reached a pressure 2.5 psi higher than the targetpressure. After the propylene oxide feed is stopped, the pressure ismaintained by continuing to regulate the carbon dioxide pressure untilthe addition of carbon dioxide is stopped. Then, the reactor is cooledto 80° C. and the reactor pressure is vented. The content of the reactoris purged with nitrogen for 30 minutes under stirring to removeunreacted propylene and carbon dioxide. The product is then cooled downto room temperature and analyzed by GPC and NMR.

TABLE 8 Initial Total amount amount Promoter of PO of PO Starter DMC 2fed fed P PO feed rate Ex. grams grams grams mL mL psig mL/min 24 272.30.0599 0.4168 34.98 661.84 175 2.5 mL/min for 70 min 2.0 mL/min for 78min 3.0 min/mi for 125 min 25 260.4 0.0611 0.3491 32.57 668.13 588 2.0mL/min for 60 min 2.3 mL/min for 84 min 2.5 min/mi for 130 min

Characteristics of Examples 24 and 25 are shown in Table 9, below

TABLE 9 CO₂ content Polyol selectivity Mn Ex. wt % wt % g/mol PDI 24 7.76 95.55 1977 1.13 25 15.56 94.81 2178 1.60

Examples 24 and 25 illustrate that the embodiments are operable atelevated pressures, but that similar polyols can be prepared at similarlevels of carbon dioxide incorporation under lower pressure operatingcondition such as those used for Example 10.

Example 26—Continuous Process of Preparing Polyols

Example 26 illustrates that the process of the embodiments is operablein a continuous polyol production process, and that polyols of varyingcarbon dioxide content can be prepared by manipulating the processconditions.

Example 26 is prepared in a 500 mL pressure reactor equipped with arecirculation loop, a mechanical agitator, and an exit port. The exitport is fitted with a heated plug flow section of tubing equal to 75 mlof volume. The pressure of the reactor is controlled at the plug flowsection exit with a control valve under the control of a process controlcomputer, which allows the reactor pressure to be maintained at aspecified pressure set point. The outlet of the reactor flows throughthe pressure control valve and into a sample collection bottle where theproduct of the reaction is collected. The reactor is also equipped witha heated external recirculation loop. The reactor contents arecirculated around the recirculation loop by means of a Micropump gearpump. The recirculation loop is equipped with a NIR flow cell which isattached to an ABB NIR analyzer. The NIR analyzer monitors the hydroxylcontent and concentration of unreacted oxirane in the reaction mixture.The recirculation loop is further equipped with injection points forpropylene oxide, ethylene oxide, carbon dioxide, glycerin (as astarter), and two separate injection points for catalysts. The oxides,carbon dioxide, and the glycerin are dispensed from storage cylindersinto the recirculation loop via Bronkhorst mass flow controllers underthe control of a process control computer.

DMC catalyst is prepared as a 2% by weight suspension in propyleneglycol. The Promoter 2 is prepared as a 10% solution in dipropoxyn-butanol (DPnB). These components are each dispensed separately intothe recirculation loop through Valco Instruments M50 model dispensingpumps at independent rates to provide the desired steady stateconcentrations of DMC catalyst and aluminum in the reaction mixture.

Feed ratios of all components are controlled to produce a polyol of thetargeted number average molecular weight, wt % carbon dioxide, wt %ethylene oxide, and wt % propylene oxide. The rates of addition arecontrolled to result in a specified residence time in the reactor.Residence time is defined as the amount of time required to feedsufficient components by weight to the reactor to completely andprecisely displace the full contents of the reactor one time.

The polyether carbonate polyol from Example No. 18 (375 grams) is placedinto the reactor. The polyol has a number average molecular weight equalto 2837 g/mol, contains 5.9% CO₂ by weight (according to the definitionprovided), and also contains 3% propylene carbonate. The polyol contains50 ppm of DMC catalyst, and 5 ppm of aluminum. The mixture is stirredand purged with nitrogen while heating to 130° C. The reactor ismaintained at 130 C with constant stirring and nitrogen purge for 90minutes to dry the reactor contents.

After the drying stage the nitrogen purge is stopped and the reactorvent is closed. The reactor pressure regulator is set to a controlpressure of 60 psig. The reactor contents are recirculated through theNIR flow cell and back into the reactor until the reactor temperatureequilibrates at 130° C. The addition of the DMC catalyst slurry (2% inMPG) is started at 11.3 microliters per minute, and the addition ofPromoter 2 (10% w/w in DPnB) is started at 12.6 microliters per minute.The addition of propylene oxide is started at a rate of 1 gram perminute for 12 minutes, then 2 grams per minute for 12 minutes, then theaddition of propylene oxide is increased to 2.67 grams per minute as theaddition of ethylene oxide is started at a rate of 0.35 grams per minuteand the addition of glycerin is started at 0.065 grams per minute. Theseflows produce a polyether polyol product with a hydroxyl equivalentweight of 1128 g/mole and a hydroxyl functionality of 2.74, containing11.1 wt % EO.

When the pressure in the reactor rises to 60 psig the pressure controlvalve on the reactor outlet opens to allow product to flow out of thereactor and into a collection bottle. The pressure control valvemaintains the reactor pressure throughout the remainder of the reactoroperation.

The addition of the oxides is maintained until 320 grams of propyleneoxide, 39 grams of ethylene oxide, and 28 grams of glycerin are added tothe reactor, at which time the propylene oxide addition rate is reducedto 2.63 grams per minute and the addition of carbon dioxide is begun ata rate of 0.04 grams per minute. All other flows are maintained asbefore. The temperature of the reactor is slowly reduced from 130° C. to110° C. over the course of 1 hour and thereafter is maintained at thattemperature. The reactor pressure is reduced to 46 psig for the lowpressure process.

These flow rates and operating conditions produce a polyol having ahydroxyl equivalent weight of approximately 1128 g/mole containing 11.1%EO by weight and 1% CO₂ by weight, in a continuous process running witha 3 hour residence time, a 75 ppm steady state concentration of DMCcatalyst and a 46 ppm steady state concentration of aluminum. Theprocess runs in a stable condition with a total unreacted oxideconcentration equal to 2.0% by weight or less.

The concurrent addition of all components is maintained for a total of70 hours, corresponding to more than 23 residence times in the reactor.The resulting product is analyzed and found to have a hydroxylequivalent weight of 1026 mg KOH/g as measured by % OH titration, anumber average molecular weight of 2950 g/mol and a polydispersity of1.16 by GPC analysis. The polyol contains 1.2% carbon dioxide by weightand 0.39% cyclic propylene carbonate by weight as determined by FTIRanalysis.

The addition rate of propylene oxide is then reduced to 2.61 grams perminute, and the carbon dioxide addition rate is increased to 0.062 gramsper minute. The DMC catalyst slurry addition rate is increased to 14microliters per minute, and the Promoter 2 solution addition rate isincreased to 15.6 microliters per minute. The reactor pressure isincreased to 50 psig. The process stabilizes and continues to run at atotal concentration of unreacted oxide of 2.0% by weight or less for 16hours, corresponding to more than 5 residence times in the reactor. Theresulting product is analyzed and found to have a percent OH value of1.63% as measured by % OH titration, a number average molecular weightof 3139 and a polydispersity of 1.16 by GPC analysis. The polyolcontains 1.5% CO₂ by weight and 0.39% cyclic propylene carbonate byweight as determined by FTIR analysis.

Polyurethane flexible foam is prepared from the polyol of Example 26according to the formulation in Table 10. The foam again is compared toa foam prepared using the same formulation with Example 26 substitutedwith VORANOL™ 8136 polyol. The formulation and properties of theresulting two foams are shown in Table 10, below.

TABLE 10 Examples 27 28 Components (parts by weight) VORANOL ™ 8136 100Polyol Example 26 100 Water 4.5 4.5 Niax ® L-618 0.6 0.6 DABCO ® BLV0.15 0.15 KOSMOS ® 29 0.2 0.2 VORANATE ™ T-80 TDI 55.0 55.0

Foam Properties for Examples 27 and 26 are shown below in Table 11.

TABLE 11 Example 27 28 Airflow-dm³/s-ASTM D 3574 G Mean (cu_ft/min) 5.895.509 CFD ISO-3386-ISO 3386/1 Mean 25% (kPa) 9.06 9.2 Mean 40% (kPa)9.85 9.95 Mean 65% (kPa) 16.31 16.34 Mean Hysteresis 46.91 44.50 CS 90%,Original, Parallel-ASTM D 3574-03/D CT (%) 3.89 3.25 CD (%) 4.30 3.59Free Rise Density-ASTM D1622-03 Density (lbm/cu_ft) 1.538 1.539 IFD:ASTM D 3574-01-Test B Load @ 25% Deflection (lbf) 42.29 44.27 Load @ 65%Deflection (lbf) 83.57 83.34 Load @ 25% Return (lbf) 26.28 28.55 SupportFactor (%) 1.98 1.88 Hysteresis (%) 62.14 64.48 Resilience (BallRebound) Test-ASTM D-3574-H Average Resiliency (%) 35.8 36.6 Tear-ASTM D3574-01 Test F-Tear test Tear strength mean (lbf/in) 2.57 2.11 Tensile:(D3574)-ASTM D 3574-01 Test E-Tensile Tensile strength mean (psi) 16.3617.19 Elongation at break (mean), % (%) 171.46 173.47

As shown in Table 11, polyols prepared using CO₂ as a co-reactant in acontinuous alkoxylation process are used to prepare flexiblepolyurethane foams with properties very similar to polyurethane foamsprepared from a similar polyol made in a continuous process, but notusing CO₂ as a co-reactant.

1-8. (canceled)
 9. A method of manufacturing a poly(ether-carbonate)polyol, comprising: a polymerization stage that includes polymerizingcarbon dioxide and at least one alkylene oxide, with a starter, in thepresence of a double metal cyanide polymerization catalyst and acatalyst promoter that is devoid of halide anions and cyanide, thecatalyst promoter being separate from the double metal cyanidepolymerization catalyst, wherein the catalyst promoter is selected fromthe group consisting of: magnesium alkyls; magnesium alkoxides;magnesium aryloxides; magnesium amides; magnesium acetylacetonate;magnesium t butylacetylacetonate; scandium alkoxides; scandiumaryloxides; scandium acetylacetonate; scandium t-butylacetylacetonate;yttrium alkoxides; yttrium aryloxides; yttrium amides; yttriumacetylacetonate; yttrium t-butylacetylacetonate; hafnium alkyls; hafniumalkoxides; hafnium aryloxides; hafnium amides; hafnium acetylacetonate;hafnium t-butylacetylacetonate; titanium alkyls; titanium aryloxides;titanium amides; titanium acetylacetonate; titaniumt-butylacetylacetonate; zirconium alkyls; zirconium alkoxides; zirconiumaryloxides; zirconium amides; zirconium acetylacetonate; zirconiumt-butylacetylacetonate; vanadium alkoxides; vanadium oxotris(alkoxides); vanadium aryloxides; vanadium tris(acetylacetonate);vanadium tris(t-butylacetylacetonate); vanadium oxobis(acetylacetonate); zinc alkyls; alkyl zinc alkoxides; zinc alkoxides;zinc aryloxides; zinc amides; zinc acetylacetonate; zinct-butylacetylacetonate; trialkyl gallium compounds; gallium alkoxides;gallium aryloxides; gallium amides; gallium acetylacetonate; galliumt-butylacetylacetonate; alkylgallium alkoxides; trialkyl indiumcompounds; indium alkoxides; indium aryloxides; indium acetylacetonate;indium t-butylacetylacetonate; stannous phosphate; stannouspyrophosphate; stannous alkoxides; stannous aryloxides; stannousacetylacetonate; and stannous t-butylacetylacetonate.
 10. The method asclaimed in claim 9, wherein the catalyst promoter is selected from thegroup consisting of: magnesium alkoxides; magnesium aryloxides;magnesium amides; magnesium acetylacetonate; magnesium tbutylacetylacetonate; scandium alkoxides; scandium aryloxides; scandiumacetylacetonate; scandium t-butylacetylacetonate; yttrium alkoxides;yttrium aryloxides; yttrium amides; yttrium acetylacetonate; yttriumt-butylacetylacetonate; hafnium alkyls; hafnium alkoxides; hafniumaryloxides; hafnium amides; hafnium acetylacetonate; hafniumt-butylacetylacetonate; titanium alkyls; titanium aryloxides; titaniumamides; titanium acetylacetonate; titanium t-butylacetylacetonate;zirconium alkyls; zirconium alkoxides; zirconium aryloxides; zirconiumamides; zirconium acetylacetonate; zirconium t-butylacetylacetonate;vanadium alkoxides; vanadium oxo tris(alkoxides); vanadium aryloxides;vanadium tris(acetylacetonate); vanadium tris(t-butylacetylacetonate);vanadium oxo bis(acetylacetonate); zinc alkyls; alkyl zinc alkoxides;zinc alkoxides; zinc aryloxides; zinc amides; zinc acetylacetonate; zinct-butylacetylacetonate; trialkyl gallium compounds; gallium alkoxides;gallium aryloxides; gallium amides; gallium acetylacetonate; galliumt-butylacetylacetonate; alkylgallium alkoxides; trialkyl indiumcompounds; indium alkoxides; indium aryloxides; indium acetylacetonate;indium t-butylacetylacetonate; stannous phosphate; stannouspyrophosphate; stannous alkoxides; stannous aryloxides; stannousacetylacetonate; and stannous t-butylacetylacetonate.
 11. The method asclaimed in claim 9, wherein the catalyst promoter is selected from thegroup consisting of: magnesium aryloxides; magnesium amides; magnesiumacetylacetonate; magnesium t butylacetylacetonate; scandium alkoxides;scandium aryloxides; scandium acetylacetonate; scandiumt-butylacetylacetonate; yttrium alkoxides; yttrium aryloxides; yttriumamides; yttrium acetylacetonate; yttrium t-butylacetylacetonate; hafniumalkyls; hafnium alkoxides; hafnium aryloxides; hafnium amides; hafniumacetylacetonate; hafnium t-butylacetylacetonate; titanium alkyls;titanium aryloxides; titanium amides; titanium acetylacetonate; titaniumt-butylacetylacetonate; zirconium alkyls; zirconium alkoxides; zirconiumaryloxides; zirconium amides; zirconium acetylacetonate; zirconiumt-butylacetylacetonate; vanadium alkoxides; vanadium oxotris(alkoxides); vanadium aryloxides; vanadium tris(acetylacetonate);vanadium tris(t-butylacetylacetonate); vanadium oxobis(acetylacetonate); zinc alkyls; alkyl zinc alkoxides; zinc alkoxides;zinc aryloxides; zinc amides; zinc acetylacetonate; zinct-butylacetylacetonate; trialkyl gallium compounds; gallium alkoxides;gallium aryloxides; gallium amides; gallium acetylacetonate; galliumt-butylacetylacetonate; alkylgallium alkoxides; trialkyl indiumcompounds; indium alkoxides; indium aryloxides; indium acetylacetonate;indium t-butylacetylacetonate; stannous phosphate; stannouspyrophosphate; stannous alkoxides; stannous aryloxides; stannousacetylacetonate; and stannous t-butylacetylacetonate.
 12. The method asclaimed in claim 9, wherein the starter includes at least one selectedfrom a mono-alcohol initiator and a poly-alcohol initiator.
 13. Themethod as claimed in claim 9, wherein in the presence of the doublemetal cyanide catalyst complex and the catalyst promoter, the carbondioxide is added intermittently or continuously during thepolymerization stage to a reactor and each alkylene oxide of the atleast one alkylene oxide is added intermittently or continuously duringthe polymerization stage to the reactor.
 14. The method as claimed inclaim 9, further comprising a preliminary stage, prior to thepolymerization stage, in which the double metal cyanide catalystcomplex, the catalyst promoter, and the starter form a starting reactionmixture.
 15. The method as claimed in claim 9, wherein the carbondioxide and the at least one alkylene oxide are polymerized with thestarter to form the poly(ether-carbonate) polyol.
 16. The method asclaimed in claim 9, wherein the poly(ether-carbonate) polyol ismanufactured in a batch or semi-batch process.
 17. The method as claimedin claim 9, wherein the poly(ether-carbonate) polyol is manufactured ina continuous process.